AVIATION GASOLINE COMPOSITIONS

Information

  • Patent Application
  • 20190345403
  • Publication Number
    20190345403
  • Date Filed
    May 10, 2019
    5 years ago
  • Date Published
    November 14, 2019
    5 years ago
  • Inventors
  • Original Assignees
    • Calumet Specialty Products Partners, L.P. (Indianapolis, IN, US)
Abstract
The present disclosure provides base aviation gasoline formulations. In addition, the present disclosure provides formulations in which one or more additives can optionally be added to the base aviation gasoline formulation to produce a finished aviation gasoline formulation.
Description
TECHNICAL FIELD

The invention relates to base aviation gasoline formulations. The invention also includes formulations in which one or more additives can optionally be added to the base aviation gasoline formulation to produce a finished aviation gasoline formulation.


BACKGROUND AND SUMMARY OF THE INVENTION

Formulations of aviation gasoline that do not require the addition of lead are highly desired by the Federal Aviation Administration and around the world. Current aviation fuels include lead in order to achieve the necessary octane levels for airplanes to achieve flight. According to the current state of the art, lead-containing additives must be added to a “base” aviation fuel blend in order to increase octane values (e.g., Motor Octane Number (MON)) of aviation gasoline. Lead is known to be detrimental to the environment and has been banned in motor fuels since the 1970s. Current aviation gasoline formulations represent the last major source of man-added lead into the environment.


A fuel that does not include harmful lead-containing additives, yet is sufficient for use in the aviation industry, is highly desirable. Ideally, such a fuel could be utilized as a “drop-in” to power existing airplane engines without modifications to the engines themselves.


Therefore, there exists a need for new formulations for use in the aviation industry that are sufficiently free of lead-containing additives. Accordingly, the present disclosure provides novel formulations of aviation gasoline that are beneficial and have numerous advantages to current formulations in the art.


The present disclosure provides base aviation gasoline formulations. In addition, the present disclosure provides formulations in which one or more additives can optionally be added to the base aviation gasoline formulation to produce a finished aviation gasoline formulation.


The formulations of aviation gasoline according to the present disclosure provide several advantages compared to other formulations known in the art. First, the disclosed formulations do not require lead-containing additives in order to achieve octane ratings sufficient for fuel standards in the airline industry. For example, the disclosed formulations can be produced with conventional technologies but meet the current ASTM D910 standards without the addition of lead. It is contemplated that a “new” ASTM specification standard without the use of lead will be identified (herein referred to as an ASTM D910-like specification) and that the disclosed formulations can be produced to meet the ASTM D910-like specification.


Second, the disclosed formulations can be produced to meet the ASTM D909 Supercharge Test. In particular, the disclosed formulations can be produced to meet the ASTM D909 Supercharge Test standards of 130 minimum.


Third, the disclosed formulations can provide benefits such as a low density and higher energy content/pound of fuel, both important considerations in the desirability of the fuel. Fourth, the disclosed formulations do not require the addition of hydrocarbon-based aromatics to the formulation and can be produced so that the formulations are substantially free of hydrocarbon-based aromatics in their final form. Hydrocarbon-based aromatics in fuels face increasing scrutiny, as a source of engine carbon deposits, increased environment toxicity due to incomplete engine combustion, higher fuel density and lower energy content, and increased carbon intensity of the fuel, leading to higher CO2 emissions.


The following numbered embodiments are contemplated and are non-limiting:

    • 1. A base aviation gasoline formulation comprising:
    • i) dimethylbutane at a concentration between about 10% to about 40%;
    • ii) trimethyl pentane at a concentration between about 50% to about 90%; and
    • iii) isobutane at a concentration between about 1% to about 5%.
    • 2. A formulation comprising the base aviation gasoline formulation of clause 1 and further comprising one or more additives.
    • 3. The formulation of clause 2, wherein the additive is selected from the group consisting of m-toluidine, methylcyclopentadienyl manganese tricarbonyl (MMT), aniline, ethyl tert-butyl ether (ETBE), a corrosion inhibitor, a lubricity additive, one or more alcohols, and any combination thereof.
    • 4. The formulation of clause 2, wherein the additive comprises m-toluidine.
    • 5. The formulation of clause 2, wherein the additive comprises methylcyclopentadienyl manganese tricarbonyl (MMT).
    • 6. The formulation of clause 2, wherein the additive comprises aniline.
    • 7. The formulation of clause 2, wherein the additive comprises ethyl tert-butyl ether (ETBE).
    • 8. The formulation of clause 2, wherein the additive comprises one or more alcohols.
    • 9. The formulation of clause 8, wherein the one or more alcohols are selected from the group consisting of ethanol, propanol, isopropanol, n-butanol, isobutanol, and any combination thereof.
    • 10. The formulation of clause 8, wherein the alcohol is ethanol.
    • 11. The formulation of clause 8, wherein the alcohol is propanol.
    • 12. The formulation of clause 8, wherein the alcohol is isopropanol.
    • 13. The formulation of clause 8, wherein the alcohol is n-butanol.
    • 14. The formulation of clause 8, wherein the alcohol is isobutanol.
    • 15. The formulation of clause 2, wherein the additives comprise m-toluidine and methylcyclopentadienyl manganese tricarbonyl (MMT).
    • 16. The formulation of clause 2, wherein the additives comprise m-toluidine and isobutanol.
    • 17. The formulation of clause 2, wherein the additive comprises m-toluidine, methylcyclopentadienyl manganese tricarbonyl (MMT), and one or more alcohols.
    • 18. The formulation of clause 17, wherein the one or more alcohols are selected from the group consisting of ethanol, propanol, isopropanol, n-butanol, isobutanol, and any combination thereof.
    • 19. The formulation of clause 17, wherein the alcohol is ethanol.
    • 20. The formulation of clause 17, wherein the alcohol is propanol.
    • 21. The formulation of clause 17, wherein the alcohol is isopropanol.
    • 22. The formulation of clause 17, wherein the alcohol is n-butanol.
    • 23. The formulation of clause 17, wherein the alcohol is isobutanol.
    • 24. The formulation of any of clauses 2 to 23, wherein addition of the one or more additives provides a MON rating to a desired MON level.
    • 25. The formulation of clause 24, wherein the desired MON level is about 99.6.
    • 26. The formulation of clause 24, wherein the desired MON level is less than 99.6 but in compliance with an ASTM D910-like specification (i.e. Specification Relief).
    • 27. The base aviation gasoline formulation of clause 1, wherein the base aviation gasoline formulation is substantially free of hydrocarbon-based aromatics.
    • 28. The base aviation gasoline formulation of clause 1, wherein the base aviation gasoline formulation does not comprise hydrocarbon-based aromatics.
    • 29. The formulation of any of clauses 2 to 26, wherein the formulation is substantially free of hydrocarbon-based aromatics.
    • 30. The formulation of any of clauses 2 to 26, wherein the formulation does not comprise hydrocarbon-based aromatics.
    • 31. A finished aviation gasoline formulation comprising:
    • i) dimethylbutane at a concentration between about 10% to about 40%;
    • ii) trimethyl pentane at a concentration between about 50% to about 90%;
    • iii) isobutane at a concentration between about 1% to about 5%, and
    • iv) two additives, wherein the two additives comprise a first additive and a second additive.
    • 32. The finished aviation gasoline formulation of clause 31, wherein the first additive is selected from the group consisting of m-toluidine, methylcyclopentadienyl manganese tricarbonyl (MMT), aniline, ethyl tert-butyl ether (ETBE), a corrosion inhibitor, a lubricity additive, one or more alcohols, and any combination thereof.
    • 33. The finished aviation gasoline formulation of clause 31, wherein the first additive is m-toluidine.
    • 34. The finished aviation gasoline formulation of clause 31, wherein the first additive is methylcyclopentadienyl manganese tricarbonyl (MMT).
    • 35. The finished aviation gasoline formulation of clause 31, wherein the first additive is aniline
    • 36. The finished aviation gasoline formulation of clause 31, wherein the first additive is ethyl tert-butyl ether (ETBE).
    • 37. The finished aviation gasoline formulation of any of clauses 31 to 36, wherein the second additive comprises one or more alcohols.
    • 38. The finished aviation gasoline formulation of any of clauses 31 to 36, wherein the second additive is selected from the group consisting of ethanol, propanol, isopropanol, n-butanol, isobutanol, and any combination thereof.
    • 39. The finished aviation gasoline formulation of any of clauses 31 to 36, wherein the second additive is ethanol.
    • 40. The finished aviation gasoline formulation of any of clauses 31 to 36, wherein the second additive is propanol.
    • 41. The finished aviation gasoline formulation of any of clauses 31 to 36, wherein the second additive is isopropanol.
    • 42. The finished aviation gasoline formulation of any of clauses 31 to 36, wherein the second additive is butanol.
    • 43. The finished aviation gasoline formulation of any of clauses 31 to 36, wherein the second additive is isobutanol.
    • 44. The finished aviation gasoline formulation of clause 31, wherein the first additive is m-toluidine and the second additive is isobutanol.
    • 45. The finished aviation gasoline formulation of any of clauses 31 to 44, wherein addition of the additives provides a MON rating to a desired MON level.
    • 46. The finished aviation gasoline formulation of clause 45, wherein the desired MON level is about 99.6.
    • 47. The finished aviation gasoline formulation of clause 45, wherein the desired MON level is less than 99.6 but in compliance with an ASTM D910-like specification (i.e. Specification Relief).
    • 48. The finished aviation gasoline formulation of any of clauses 31 to 47, wherein the finished aviation gasoline formulation is substantially free of hydrocarbon-based aromatics.
    • 49. The finished aviation gasoline formulation of any of clauses 31 to 47, wherein the finished aviation gasoline formulation does not comprise hydrocarbon-based aromatics.


BRIEF DESCRIPTION OF THE DRAWINGS

Various embodiments of the invention are described herein as follows. In one embodiment described herein, a base aviation gasoline formulation is provided wherein the base aviation gasoline formulation comprises i) dimethylbutane at a concentration between about 10% to about 40%; ii) trimethyl pentane at a concentration between about 50% to about 90%; and iii) isobutane at a concentration between about 1% to about 5%. All percentages listed in the present disclosure refer to volume percentages, unless otherwise noted.


In another embodiment, a finished aviation gasoline formulation is provided wherein the finished aviation gasoline formulation comprises i) dimethylbutane at a concentration between about 10% to about 40%; ii) trimethyl pentane at a concentration between about 50% to about 90%; iii) isobutane at a concentration between about 1% to about 5%, and iv) two additives, wherein the two additives comprise a first additive and a second additive.


In the various embodiments, the base aviation gasoline formulation comprises dimethylbutane. Dimethylbutane is well known in the art as an alkane and has the formula C6H14. In particular, the structure of dimethylbutane can comprise either 2,3-dimethylbutane or 2,2-dimethylbutane, each of which are depicted below:




embedded image


In various embodiments, the dimethylbutane comprises 2,3-dimethylbutane. In other embodiments, the dimethylbutane comprises 2,2-dimethylbutane. In some embodiments, the dimethylbutane comprises 2,3-dimethylbutane and 2,2-dimethylbutane.


In various embodiments, the dimethylbutane consists essentially of 2,3-dimethylbutane. In other embodiments, the dimethylbutane consists essentially of 2,2-dimethylbutane. In some embodiments, the dimethylbutane consists essentially of 2,3-dimethylbutane and 2,2-dimethylbutane.


In various embodiments, the dimethylbutane consists of 2,3-dimethylbutane. In other embodiments, the dimethylbutane consists of 2,2-dimethylbutane. In some embodiments, the dimethylbutane consists of 2,3-dimethylbutane and 2,2-dimethylbutane.


In certain aspects, the dimethylbutane is present in the base aviation gasoline formulation at a concentration between about 10% to about 40%. In some embodiments, the dimethylbutane is present in the base aviation gasoline formulation at a concentration between about 15% to about 35%. In other embodiments, the dimethylbutane is present in the base aviation gasoline formulation at a concentration between about 20% to about 30%.


In certain aspects, the dimethylbutane is present in the base aviation gasoline formulation at a concentration of about 10%. In certain aspects, the dimethylbutane is present in the base aviation gasoline formulation at a concentration of about 15%. In certain aspects, the dimethylbutane is present in the base aviation gasoline formulation at a concentration of about 20%. In certain aspects, the dimethylbutane is present in the base aviation gasoline formulation at a concentration of about 25%. In certain aspects, the dimethylbutane is present in the base aviation gasoline formulation at a concentration of about 30%. In certain aspects, the dimethylbutane is present in the base aviation gasoline formulation at a concentration of about 35%. In certain aspects, the dimethylbutane is present in the base aviation gasoline formulation at a concentration of about 40%.


In the various embodiments, the dimethylbutane can include 2,3-dimethylbutane and/or 2,2-dimethylbutane in any quantity to comprise the stated concentration of dimethylbutane.


In the various embodiments, the base aviation gasoline formulation comprises any of the isomers of trimethyl pentane, individually or in any combination. Trimethyl pentane has the formula (CH3)3CCH2CH(CH3)2. For instance, the structure of one isomer of trimethyl pentane is as follows:




embedded image


In certain aspects, the trimethyl pentane is present in the base aviation gasoline formulation at a concentration between about 50% to about 90%. In some embodiments, the trimethyl pentane is present in the base aviation gasoline formulation at a concentration between about 60% to about 80%. In other embodiments, the trimethyl pentane is present in the base aviation gasoline formulation at a concentration between about 60% to about 70%. In other embodiments, the trimethyl pentane is present in the base aviation gasoline formulation at a concentration between about 70% to about 80%.


In certain aspects, the trimethyl pentane is present in the base aviation gasoline formulation at a concentration of about 50%. In certain aspects, the trimethyl pentane is present in the base aviation gasoline formulation at a concentration of about 55%. In certain aspects, the trimethyl pentane is present in the base aviation gasoline formulation at a concentration of about 60%. In certain aspects, the trimethyl pentane is present in the base aviation gasoline formulation at a concentration of about 65%. In certain aspects, the trimethyl pentane is present in the base aviation gasoline formulation at a concentration of about 70%. In certain aspects, the trimethyl pentane is present in the base aviation gasoline formulation at a concentration of about 75%. In certain aspects, the trimethyl pentane is present in the base aviation gasoline formulation at a concentration of about 80%. In certain aspects, the trimethyl pentane is present in the base aviation gasoline formulation at a concentration of about 85%. In certain aspects, the trimethyl pentane is present in the base aviation gasoline formulation at a concentration of about 90%.


In certain aspects, the trimethyl pentane is present in the base aviation gasoline formulation at a concentration of about 65%. In certain aspects, the trimethyl pentane is present in the base aviation gasoline formulation at a concentration of about 65.5%. In certain aspects, the trimethyl pentane is present in the base aviation gasoline formulation at a concentration of about 66%. In certain aspects, the trimethyl pentane is present in the base aviation gasoline formulation at a concentration of about 66.5%. In certain aspects, the trimethyl pentane is present in the base aviation gasoline formulation at a concentration of about 67%. In certain aspects, the trimethyl pentane is present in the base aviation gasoline formulation at a concentration of about 67.5%. In certain aspects, the trimethyl pentane is present in the base aviation gasoline formulation at a concentration of about 68%. In certain aspects, the trimethyl pentane is present in the base aviation gasoline formulation at a concentration of about 68.5%. In certain aspects, the trimethyl pentane is present in the base aviation gasoline formulation at a concentration of about 69%. In certain aspects, the trimethyl pentane is present in the base aviation gasoline formulation at a concentration of about 69.5%. In certain aspects, the trimethyl pentane is present in the base aviation gasoline formulation at a concentration of about 70%. In certain aspects, the trimethyl pentane is present in the base aviation gasoline formulation at a concentration of about 70.5%. In certain aspects, the trimethyl pentane is present in the base aviation gasoline formulation at a concentration of about 71%. In certain aspects, the trimethyl pentane is present in the base aviation gasoline formulation at a concentration of about 71.5%. In certain aspects, the trimethyl pentane is present in the base aviation gasoline formulation at a concentration of about 72%. In certain aspects, the trimethyl pentane is present in the base aviation gasoline formulation at a concentration of about 72.5%. In certain aspects, the trimethyl pentane is present in the base aviation gasoline formulation at a concentration of about 73%. In certain aspects, the trimethyl pentane is present in the base aviation gasoline formulation at a concentration of about 73.5%. In certain aspects, the trimethyl pentane is present in the base aviation gasoline formulation at a concentration of about 74%. In certain aspects, the trimethyl pentane is present in the base aviation gasoline formulation at a concentration of about 74.5%. In certain aspects, the trimethyl pentane is present in the base aviation gasoline formulation at a concentration of about 75%. In certain aspects, the trimethyl pentane is present in the base aviation gasoline formulation at a concentration of about 75.5%. In certain aspects, the trimethyl pentane is present in the base aviation gasoline formulation at a concentration of about 76%. In certain aspects, the trimethyl pentane is present in the base aviation gasoline formulation at a concentration of about 76.5%. In certain aspects, the trimethyl pentane is present in the base aviation gasoline formulation at a concentration of about 77%. In certain aspects, the trimethyl pentane is present in the base aviation gasoline formulation at a concentration of about 77.5%. In certain aspects, the trimethyl pentane is present in the base aviation gasoline formulation at a concentration of about 78%. In certain aspects, the trimethyl pentane is present in the base aviation gasoline formulation at a concentration of about 78.5%. In certain aspects, the trimethyl pentane is present in the base aviation gasoline formulation at a concentration of about 79%. In certain aspects, the trimethyl pentane is present in the base aviation gasoline formulation at a concentration of about 79.5%. In certain aspects, the trimethyl pentane is present in the base aviation gasoline formulation at a concentration of about 80%.


In the various embodiments, the base aviation gasoline formulation comprises isobutane. Isobutane, also known as i-butane, 2-methylpropane or methylpropane, has the formula HC(CH3)3. For instance, the structure of isobutane is as follows:




embedded image


In certain aspects, the isobutane is present in the base aviation gasoline formulation at a concentration between about 1% to about 5%. In some embodiments, the isobutane is present in the base aviation formulation at a concentration between about 2% to about 5%. In some embodiments, the isobutane is present in the base aviation formulation at a concentration between about 3% to about 4%. In some embodiments, the isobutane is present in the base aviation formulation at a concentration between about 2% to about 4%.


In some embodiments, the isobutane is present in the base aviation formulation at a concentration of about 2%. In some embodiments, the isobutane is present in the base aviation formulation at a concentration of about 2.1%. In some embodiments, the isobutane is present in the base aviation formulation at a concentration of about 2.2%. In some embodiments, the isobutane is present in the base aviation formulation at a concentration of about 2.3%. In some embodiments, the isobutane is present in the base aviation formulation at a concentration of about 2.4%. In some embodiments, the isobutane is present in the base aviation formulation at a concentration of about 2.5%. In some embodiments, the isobutane is present in the base aviation formulation at a concentration of about 2.6%. In some embodiments, the isobutane is present in the base aviation formulation at a concentration of about 2.7%. In some embodiments, the isobutane is present in the base aviation formulation at a concentration of about 2.8%. In some embodiments, the isobutane is present in the base aviation formulation at a concentration of about 2.9%.


In some embodiments, the isobutane is present in the base aviation formulation at a concentration of about 3%. In some embodiments, the isobutane is present in the base aviation formulation at a concentration of about 3.1%. In some embodiments, the isobutane is present in the base aviation formulation at a concentration of about 3.2%. In some embodiments, the isobutane is present in the base aviation formulation at a concentration of about 3.3%. In some embodiments, the isobutane is present in the base aviation formulation at a concentration of about 3.4%. In some embodiments, the isobutane is present in the base aviation formulation at a concentration of about 3.5%. In some embodiments, the isobutane is present in the base aviation formulation at a concentration of about 3.6%. In some embodiments, the isobutane is present in the base aviation formulation at a concentration of about 3.7%. In some embodiments, the isobutane is present in the base aviation formulation at a concentration of about 3.8%. In some embodiments, the isobutane is present in the base aviation formulation at a concentration of about 3.9%.


In some embodiments, the isobutane is present in the base aviation formulation at a concentration of about 4%. In some embodiments, the isobutane is present in the base aviation formulation at a concentration of about 4.1%. In some embodiments, the isobutane is present in the base aviation formulation at a concentration of about 4.2%. In some embodiments, the isobutane is present in the base aviation formulation at a concentration of about 4.3%. In some embodiments, the isobutane is present in the base aviation formulation at a concentration of about 4.4%. In some embodiments, the isobutane is present in the base aviation formulation at a concentration of about 4.5%. In some embodiments, the isobutane is present in the base aviation formulation at a concentration of about 4.6%. In some embodiments, the isobutane is present in the base aviation formulation at a concentration of about 4.7%. In some embodiments, the isobutane is present in the base aviation formulation at a concentration of about 4.8%. In some embodiments, the isobutane is present in the base aviation formulation at a concentration of about 4.9%.


In another aspect, a formulation is provided comprising the base aviation gasoline formulation and further comprises one or more additives. The formulations herein can include one additive or multiple additives.


The additive(s) may be combined with the base aviation fuel formulation, or with any components of the base aviation fuel formulation, in any order to result in the formulation. In certain aspects, when additive(s) are combined with the base aviation gasoline formulation, the resultant formulation is considered to be a finished aviation gasoline formulation.


In certain aspects, the additive is selected from the group consisting of m-toluidine, methylcyclopentadienyl manganese tricarbonyl (MMT), aniline, ethyl tert-butyl ether (ETBE), a corrosion inhibitor, a lubricity additive, one or more alcohols, and any combination thereof. In various embodiments, the additive comprises a corrosion inhibitor. In some embodiments, the corrosion inhibitor is selected from the group consisting of DCI-4A, DCI-6A, HITEC 580, NALCO 5403, NALCO 5405, PRI-19, UNICOR J, SPEC-AID 8Q22, TOLAD 351, TOLAD 4410, NALCO EC5407A, and any combination thereof. In other embodiments, the additive comprises a lubricity additive. In some embodiments, the lubricity additive is selected from the group consisting of Nalco5407A, Lubrizol, Infinium, Innospec, Afton MCC, and any combination thereof.


In another aspect, the additive comprises one or more alcohols. In some embodiments, the one or more alcohols are selected from the group consisting of ethanol, propanol, isopropanol, n-butanol, isobutanol, and any combination thereof. Without being bound to any theory, the alcohols may be combined with the base aviation gasoline formulation, which optionally comprises another additive, in order to address cold flow properties.


Concentrations of the one or more additives described herein refer to each additive individually in relation to the total volume of the formulation or to the total volume of the finished aviation gasoline formulation. In certain aspects, the additive is present in the formulation at a concentration between about 0.001% to about 5%. In some embodiments, the additive is present in the formulation at a concentration between about 0.01% to about 5%. In some embodiments, the additive is present in the formulation at a concentration between about 0.1% to about 5%. In some embodiments, the additive is present in the formulation at a concentration between about 1% to about 5%. In some embodiments, the additive is present in the formulation at a concentration between about 1% to about 5%. In some embodiments, the additive is present in the formulation at a concentration between about 2% to about 4%.


In some embodiments, the additive is present in the formulation at a concentration of about 2%. In some embodiments, the additive is present in the formulation at a concentration of about 2.1%. In some embodiments, the additive is present in the formulation at a concentration of about 2.2%. In some embodiments, the additive is present in the formulation at a concentration of about 2.3%. In some embodiments, the additive is present in the formulation at a concentration of about 2.4%. In some embodiments, the additive is present in the formulation at a concentration of about 2.5%. In some embodiments, the additive is present in the formulation at a concentration of about 2.6%. In some embodiments, the additive is present in the formulation at a concentration of about 2.7%. In some embodiments, the additive is present in the formulation at a concentration of about 2.8%. In some embodiments, the additive is present in the formulation at a concentration of about 2.9%.


In some embodiments, the additive is present in the formulation at a concentration of about 3%. In some embodiments, the additive is present in the formulation at a concentration of about 3.1%. In some embodiments, the additive is present in the formulation at a concentration of about 3.2%. In some embodiments, the additive is present in the formulation at a concentration of about 3.3%. In some embodiments, the additive is present in the formulation at a concentration of about 3.4%. In some embodiments, the additive is present in the formulation at a concentration of about 3.5%. In some embodiments, the additive is present in the formulation at a concentration of about 3.6%. In some embodiments, the additive is present in the formulation at a concentration of about 3.7%. In some embodiments, the additive is present in the formulation at a concentration of about 3.8%. In some embodiments, the additive is present in the formulation at a concentration of about 3.9%.


In some embodiments, the additive is present in the formulation at a concentration of about 4%. In some embodiments, the additive is present in the formulation at a concentration of about 4.1%. In some embodiments, the additive is present in the formulation at a concentration of about 4.2%. In some embodiments, the additive is present in the formulation at a concentration of about 4.3%. In some embodiments, the additive is present in the formulation at a concentration of about 4.4%. In some embodiments, the additive is present in the formulation at a concentration of about 4.5%. In some embodiments, the additive is present in the formulation at a concentration of about 4.6%. In some embodiments, the additive is present in the formulation at a concentration of about 4.7%. In some embodiments, the additive is present in the formulation at a concentration of about 4.8%. In some embodiments, the additive is present in the formulation at a concentration of about 4.9%.


In certain embodiments, addition of the one or more additives provides a Motor Octane Number (MON) rating to a desired MON level. Methods of determining MON rating are well known in the art and typically utilize an engine speed of 900 rpm. In some instances, the desired MON level is about 99.6. However, in other embodiments, the desired MON level is less than 99.6 but in compliance with an ASTM D910-like specification (i.e. Specification Relief). The ASTM 910 is an existing specification for leaded aviation gasolines and is well known to the skilled artisan. Further, it is contemplated that a “new” ASTM specification standard without the use of lead will be identified (herein referred to as an ASTM D910-like specification) and that the disclosed formulations will meet the ASTM D910-like specification.


In some aspects, the base aviation gasoline formulation is substantially free of hydrocarbon-based aromatics. As used herein, aromatics refers to hydrocarbon-based aromatics. In some aspects, the formulation is substantially free of hydrocarbon-based aromatics. As used herein, the term “substantially free” refers to zero or nearly no detectable amount of a material, quantity, or item. For example, the amount can be less than 2 percent, less than 0.5 percent, or less than 0.1 percent of the material, quantity, or item. In some embodiments, the base aviation gasoline formulation does not comprise hydrocarbon-based aromatics. In some embodiments, the formulation does not comprise hydrocarbon-based aromatics.


In another aspect of the present disclosure, a finished aviation gasoline formulation is provided, wherein the finished aviation gasoline formulation comprises i) dimethylbutane at a concentration between about 10% to about 40%; ii) trimethyl pentane at a concentration between about 50% to about 90%; iii) isobutane at a concentration between about 1% to about 5%, and iv) two additives, wherein the two additives comprise a first additive and a second additive. The previously described embodiments of the base aviation gasoline formulation, and to the formulation comprising the base aviation gasoline formulation further comprising one or more additives, are also applicable to the finished aviation gasoline formulation described herein.


The finished aviation gasoline formulation comprises two additives, wherein the two additives comprise a first additive and a second additive. The first additive may be present in the finished aviation gasoline formulation at a concentration between about 0.001% to about 5%, relative to the total volume of the finished aviation gasoline formulation. The second additive may be present in the finished aviation gasoline formulation at a concentration between about 0.001% to about 5%, relative to the total volume of the finished aviation gasoline formulation. Any concentration of additive as previously described for the formulation of base aviation gasoline formulation further comprising one or more additives are also applicable to the finished aviation gasoline formulation.







EXAMPLE 1
Preparation of Formulations

In one exemplary embodiment, the base aviation gasoline formulation comprises the following: dimethylbutane at 25%; trimethyl pentane at 71.5%; and isobutane at 3.5%. All percentages listed refer to volume percentages, unless otherwise noted.


The base aviation gasoline formulation can be combined with one or more additives to produce a finished aviation gasoline formulation that meet current ASTM D910 specifications. For example, a finished aviation gasoline formulation can comprise i) the base aviation gasoline formulation comprising dimethylbutane at 25%; trimethyl pentane at 71.5%; and isobutane at 3.5% and ii) m-toluidine at 2.0%. The percentage of components for this exemplary finished aviation gasoline formulation is thus as shown in Table 1:


In another example, a finished aviation gasoline formulation can comprise i) the base aviation gasoline formulation comprising dimethylbutane at 25%; trimethyl pentane at 71.5%; and isobutane at 3.5%, ii) m-toluidine at 2.0%, and iii) isobutanol at 3.0%. The percentage of components for this exemplary finished aviation gasoline product is as shown in Table 2:


EXAMPLE 2
Evaluation of Exemplary Formulations

In this example, various formulations were evaluated for distillation characteristics and other properties according to known ASTM evaluation methods. Five different formulations were evaluated and the results are presented in Table 3 and Table 4 below. All percentages listed refer to volume percentages, unless otherwise noted.















TABLE 3







GD170738







Second Lab
GD170738


GD170738 60-



Blend
First Lab Blend
GD161554
GD170738
40





















2,2-




15


Dimethylbutane


2,3-
25.0
25.0
25.0
25.0
10


Dimethylbutane


Isopentane
71.5
71.5
71.5
71.5
71.5


Toluene


Trimethyl Pentane


Isobutane
3.5
3.5
3.5
3.5
3.5


Base fuel
100.0
100.0
100.0
100.0
100.0


m-Toluidine
2.00%
2.00%
0%
2.00%
2.00%
























TABLE 4















GD170738






GD170738
GD170738

GD170738
60-40






Second Lab
First Lab

ChemCAD
ChemCAD






Blend
Blend
GD161554
Simulation
Simulation





Specifications
2% m-
2% m-
0% m-
2% m-
2% m-
















Test
Method
Unit
MIN
MAX
Toluidine
Toluidine
Toluidine
Toluidine
Toluidine



















Distillation, %
ASTM D86
° C.


41.4
41.7
39.5
59.7
56.9


Evap-IBP











 5%

° C.



67.8
66.8
69.0
65.8


10%

° C.

75
75.2
75.6
74.8
75.6
72.4


20%

° C.



82.2
81.6
82.8
80.5


30%

° C.



86.0
84.9
86.6
85.3


40%

° C.
75

88.5
89.1
87.9
89.7
89.4


50%

° C.

105
91.5
92.4
90.9
92.8
93.2


60%

° C.



95.3
93.7
95.8
96.5


70%

° C.



97.6
95.9
98.5
99.2


80%

° C.



99.6
97.2
100.7
101.1


90%

° C.

135
100.3
101.4
97.7
102.5
102.6


95%

° C.



102.8
97.8
103.7
103.7


Distillation-EP

° C.

170
178.2
132.2
103.0
109.4
109.4


Recovery

vol %
97.0

97.1
96.7
97.8




Residue

vol %

1.5
1.1
2.1
0.9




Loss

vol %

1.5
1
1.2
1.3




T10 + T50
ASTM D86
° C.
135.0

166.7
168.0

168.4



Reid Vapor
ASTM D5191
kPa
38
49
45.4
43.55
43.55




Pressure, E,











(ASTM)











Freeze Point
ASTM D2386
° C.

−58.0







(Dixie)











Freeze Point
ASTM D2386
° C.

−58







(Haltermann)











Motor Octane
ASTM D2700



100.4
100.4
97.4




Number











Supercharge
ASTM D910



132.5









EXAMPLE 3
Analysis of Exemplary Formulations

In this example, an exemplary gasoline formulations was analyzed for compliance with the requirements for Grade 100LL detailed in Table 1 of ASTM D910-17a, entitled “Standard Specification for Leaded Aviation Gasolines.” The results of the analysis are presented in Table 5 and Table 6. All percentages listed refer to volume percentages, unless otherwise noted.












TABLE 5







Subject



Test
Property
Sample
Grade 100LL


















D3338
Net heat of combustion,
44.460
 43.5 MIN



MJ/kg


D2700
Knock value, lean mixture



Motor Octane Number
100.4
 99.6 MIN



Aviation Lean Rating
102.1
100.0 MIN


D909
Knock value, rich mixture



Performance number
135.2
130.0 MIN


D2622
Sulfur, mass percent
<0.0001
 0.05 MAX


D5059(c)
Tetraethyl lead, g Pb/L
<0.005
0.28 MIN, 0.56 MAX


D2392
Color
Any
Blue



















TABLE 6





Test
Property
Subject Sample
All Grades


















D5191
Vapor pressure, 38° C., kPa
45.4
38.0 MIN,





49.0 MAX


D4052
Density at 15° C., kg/m3
691.0
REPORT


D86
Distillation, ° C.



Initial boiling point
41.4
REPORT



Fuel Evaporated












10 volume percent at ° C.
75.2
75
MAX



40 volume percent at ° C.
88.5
75
MIN



50 volume percent at ° C.
91.5
105
MAX



90 volume percent at ° C.
100.3
135
MAX



Final boiling point
178.2
170
MAX



Sum of 10% + 50%
166.7
135
MIN



evaporated temperatures



Recovery volume percent
97.9
97
MIN



Residue volume percent
1.1
1.5
MAX



Loss volume percent
1.0
1.5
MAX


D2386
Freezing point, ° C.
nd
−58
MAX


D130
Copper strip, 2 h at 100° C.
3a
No. 1
MAX


D873
Oxidation stability, mg/100 mL



(5 h aging)



Potential gum
3
6
MAX



Lead precipitate
<0.1
3
MAX


D1094
Water reaction



Volume change, mL
0.0
+/−2
MAX


D2624
Electrical conductivity, pSm
3
450
MAX









Regarding test D2386, behavior of the sample was atypical compared to normal hydrocarbon fuels. Analyst observations of the subject sample are summarized below. The temperature when the particles disappear is recorded as the observed freezing point.


On cooling:


















Haze consistent throughout the sample
−19



Sample removed from cooling bath
−19










On warming:


















Haze disappears
−17










EXAMPLE 4
Analysis of Co-Solvent Additives

In various embodiments, a co-solvent additive can be included in the finished aviation gasoline formulation in order to address cold flow properties of the formulation. For example, a co-solvent additive such as an alcohol can be added in this regard.


This example provides a protocol for evaluation of various alcohols as co-solvents. In particular, alcohols can be added to the base aviation gasoline formulation (e.g., at 3% vol) and evaluated for i) MON, ii) T10, and iii) freezing point. The resultant analysis can provide the best alcohol or alcohols for achieving desirable cold flow properties of the formulation.

Claims
  • 1. A base aviation gasoline formulation comprising: i) dimethylbutane at a concentration between about 10% to about 40%;ii) trimethyl pentane at a concentration between about 50% to about 90%; andiii) isobutane at a concentration between about 1% to about 5%.
  • 2. A formulation comprising the base aviation gasoline formulation of claim 1 and further comprising one or more additives.
  • 3. The formulation of claim 2, wherein the additive is selected from the group consisting of m-toluidine, methylcyclopentadienyl manganese tricarbonyl (MMT), aniline, ethyl tert-butyl ether (ETBE), a corrosion inhibitor, a lubricity additive, one or more alcohols, and any combination thereof.
  • 4. The formulation of claim 2, wherein the additive comprises m-toluidine.
  • 5. The formulation of claim 2, wherein the additive comprises one or more alcohols.
  • 6. The formulation of claim 5, wherein the one or more alcohols are selected from the group consisting of ethanol, propanol, isopropanol, n-butanol, isobutanol, and any combination thereof.
  • 7. The formulation of claim 5, wherein the alcohol is isobutanol.
  • 8. The formulation of claim 2, wherein the additives comprises m-toluidine and isobutanol.
  • 9. The formulation of claim 2, wherein addition of the one or more additives provides a MON rating to a desired MON level, wherein the desired MON level is about 99.6.
  • 10. The base aviation gasoline formulation of claim 1, wherein the formulation is substantially free of hydrocarbon-based aromatics.
  • 11. A finished aviation gasoline formulation comprising: i) dimethylbutane at a concentration between about 10% to about 40%;ii) trimethyl pentane at a concentration between about 50% to about 90%;iii) isobutane at a concentration between about 1% to about 5%, andiv) two additives, wherein the two additives comprise a first additive and a second additive.
  • 12. The finished aviation gasoline formulation of claim 11, wherein the first additive is selected from the group consisting of m-toluidine, methylcyclopentadienyl manganese tricarbonyl (MMT), aniline, ethyl tert-butyl ether (ETBE), a corrosion inhibitor, a lubricity additive, one or more alcohols, and any combination thereof.
  • 13. The finished aviation gasoline formulation of claim 11, wherein the first additive is m-toluidine.
  • 14. The finished aviation gasoline formulation of claim 11, wherein the second additive comprises one or more alcohols.
  • 15. The finished aviation gasoline formulation of claim 11, wherein the second additive is selected from the group consisting of ethanol, propanol, isopropanol, n-butanol, isobutanol, and any combination thereof.
  • 16. The finished aviation gasoline formulation of claim 11, wherein the second additive is isobutanol.
  • 17. The finished aviation gasoline formulation of claim 11, wherein the first additive is m-toluidine and the second additive is isobutanol.
  • 18. The finished aviation gasoline formulation of claim 11, wherein addition of the additives provides a MON rating to a desired MON level, wherein the desired MON level is about 99.6.
  • 19. The finished aviation gasoline formulation of claim 11, wherein addition of the additives provides a MON rating to a desired MON level, wherein the desired MON level is less than 99.6 but in compliance with an ASTM D910-like specification (i.e. Specification Relief).
  • 20. The finished aviation gasoline formulation of claim 11, wherein the formulation is substantially free of hydrocarbon-based aromatics.
CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit under 35 USC § 119(e) of U.S. Provisional Application Ser. No. 62/669,706, filed on May 10, 2018, the entire disclosure of which is incorporated herein by reference.

Provisional Applications (1)
Number Date Country
62669706 May 2018 US