Patent Grant
10087383
This invention relates to aviation fuel additives and specifically to a scavenger mixed and used in the additive and eventual fuel compositions. The scavenger is used together with a manganese-containing additive component to reduce and/or modify the formation of engine deposits otherwise caused by the combustion of the aviation fuel.
Current and future regulations with respect to aviation fuel compositions include a no-lead requirement. Aviation fuel compositions therefore, are challenged to include components that replace the positive performance features that are a result from the incorporation of lead in aviation fuels. These challenges include meeting the rating number octane requirements of an aviation fuel composition and managing engine deposits that result from the combustion of new formulations of aviation fuels, including but not limited to manganese-containing additives. Unfortunately, the solution for some of these performance specifications can cause problems with respect to other performance specifications. The unique aviation fuel requirements present these previously unsolved challenges.
Accordingly, it is an objective of the present invention to overcome the challenges with formulating new aviation fuel compositions that include manganese-containing compounds. In one example, an aviation fuel additive composition comprises a cyclopentadienyl manganese tricarbonyl compound and a manganese scavenger compound. The manganese scavenger compound may comprise a phosphorus-containing compound, an organobromide compound, or a tricarbonyl compound. The phosphorus-containing compound may be selected from the group consisting of tritolyl phosphate, triphenyl phosphate, triisopropyl phosphate, dimethyl methyl phosphonate, triphenyl phosphine oxide, and triphenyl phosphine. The organobromide compound may be selected from the group consisting of 1,2-dibromoethane; 3,5-dibromotoluene; 2,5-dibromotoluene; and 2,6-dibromo-4-methylaniline. And the manganese scavenger may be comprised of a tricarbonyl compound selected from the group consisting of glycerol triacetate; triethyl 1,1,2-ethanetricarboxylate; triethyl citrate, and tributyl citrate. The cyclopentadienyl manganese tricarbonyl may comprise methylcyclopentadienyl manganese tricarbonyl. The amount of methylcyclopentadienyl manganese tricarbonyl may equal about 1 to 500 mg/l of the additive composition.
A method of reducing manganese-containing deposits that result from the combustion of an aviation fuel including a cyclopentadienyl manganese tricarbonyl includes several steps. First, at least one scavenger provided is selected from the group consisting of phosphorus-containing compound, an organobromide compound, or a tricarbonyl compound. This scavenger is then mixed with a substantially lead-free aviation fuel composition that further comprises a cyclopentadienyl manganese tricarbonyl. The fuel and scavenger mixture is then combusted in an aviation fuel, spark ignition engine, wherein the combustion results in less and/or modified engine deposits than the combustion of a fuel composition without a scavenger in a comparable engine.
Use of any fuel additives in connection with aviation fuel compositions can be and often is different from the use of additives in connection with vehicle motor fuels. In vehicle fuels, there is a great concern with respect to engine emissions. In aviation fuels, an emphasis is consistent and reliable engine performance. This sometimes-different emphasis means advances in one type of fuel formulation can be different from and counterintuitive to those different formulations as they may not be applicable in the other setting.
The present invention is a scavenger used in aviation fuel compositions and additives used to formulate finished aviation fuel compositions. Specifically, the purpose of the scavenger described herein is to scavenge manganese, and specifically thereby reduce and/or modify the manganese-containing engine deposits that can form in spark-ignited aviation engines. By reducing or modifying the manganese-containing deposits, for instance manganese oxide deposits, the aviation engine performance is made more consistent and reliable.
The aviation fuels relevant to the discussion herein also include manganese-containing additives. These additives are typically, but not limited to, cyclopentadienyl manganese tricarbonyl compounds.
Cyclopentadienyl manganese tricarbonyl compounds which can be used in the practice of the fuels herein include cyclopentadienyl manganese tricarbonyl, methylcyclopentadienyl manganese tricarbonyl, dimethylcyclopentadienyl manganese tricarbonyl, trimethylcyclopentadienyl manganese tricarbonyl, tetramethylcyclopentadienyl manganese tricarbonyl, pentamethylcyclopentadienyl manganese tricarbonyl, ethylcyclopentadienyl manganese tricarbonyl, diethylcyclopentadienyl manganese tricarbonyl, propylcyclopentadienyl manganese tricarbonyl, isopropylcyclopentadienyl manganese tricarbonyl, tertbutylcyclopentadienyl manganese tricarbonyl, octylcyclopentadienyl manganese tricarbonyl, dodecylcyclopentadienyl manganese tricarbonyl, ethylmethylcyclopentadienyl manganese tricarbonyl, indenyl manganese tricarbonyl, and the like, including mixtures of two or more such compounds. Preferred are the cyclopentadienyl manganese tricarbonyls which are liquid at room temperature such as methylcyclopentadienyl manganese tricarbonyl, ethylcyclopentadienyl manganese tricarbonyl, liquid mixtures of cyclopentadienyl manganese tricarbonyl and methylcyclopentadienyl manganese tricarbonyl, mixtures of methylcyclopentadienyl manganese tricarbonyl and ethylcyclopentadienyl manganese tricarbonyl, etc. The aviation fuels of this invention will contain an amount of one or more of the foregoing cyclopentadienyl manganese tricarbonyl compounds sufficient to provide the requisite octane number and valve seat wear performance characteristics.
For the purposes of this application, a fuel composition is described in ASTM 4814 as substantially “lead-free” or “unleaded” if it contains 13 mg of lead or less per liter (or about 50 mg Pb/gal or less) of lead in the fuel. Alternatively, the terms “lead-free” or “unleaded” mean about 7 mg of lead or less per liter of fuel. Still further alternatively, it means an essentially undetectable amount of lead in the fuel composition. In other words, there can be trace amounts of lead in a fuel; however, the fuel is essentially free of any detectable amount of lead. It is to be understood that the fuels are unleaded in the sense that a lead-containing antiknock agent is not deliberately added to the gasoline. Trace amounts of lead due to contamination of equipment or like circumstances are permissible and are not to be deemed excluded from the fuels described herein.
The aviation fuel composition as described herein typically contains aviation alkylate components. Those components may comprise about 10 to 80 volume percent of the fuel. Aromatic hydrocarbons may be incorporated into the fuel to improve the octane rating of the fuel. These aromatic hydrocarbons are incorporated according to one example of the present invention at a rate of about zero to 30 volume percent of the fuel composition. In another example, the aromatic hydrocarbons are incorporated at a rate of about 10 to 20 volume percent of the fuel composition.
The fuel blend may contain aromatic gasoline hydrocarbons, at least a major proportion of which are mononuclear aromatic hydrocarbons such as toluene, xylenes, the mesitylenes, ethyl benzene, etc. Mesitylene is particularly preferred in one embodiment. Other suitable optional gasoline hydrocarbon components that can be used in formulating the aviation fuels described herein include isopentane, light hydrocracked gasoline fractions, and/or C5-6 gasoline isomerate.
Other components which can be employed, and under certain circumstances are preferably employed, include dyes which do not contribute to excessive induction system deposits. Typical dyes which can be employed are 1,4-dialkylaminoanthraquinone, p-diethylaminoazobenzene (Color Index No. 11020) or Color Index Solvent Yellow No. 107, methyl derivatives of azobenzene-4-azo-2-naphthol (methyl derivatives of Color Index No. 26105), alkyl derivatives of azobenzene-4-azo-2-naphthol, or equivalent materials. The amounts used should, wherever possible, conform to the limits specified in ASTM Specification D 910-90.
The amount of manganese-containing additives can be varied according to the base fuels and the other additives being incorporated with the fuel. It is expected that the amount of manganese added is in the range of about 1 to 500 mg Mn/l of the finished fuel, or alternatively about 5 to 250 mg Mn/l, or still further alternatively about 125 to 225 mg Mn/l. The additive concentration will vary depending on the target concentration of the end fuel composition and the relative volume amounts of additive and base fuel being combined.
The manganese scavenger compound may be any compound that interacts with the manganese-containing additive component. By “scavenging” herein is meant the contacting, combining with, reacting, incorporating, chemically bonding with or to, physically bonding with or to, adhering to, agglomerating with, affixing, inactivating, rendering, inert, consuming, alloying, gathering, cleansing, consuming, or any other way or means whereby a first material makes a second material unavailable or less available. Examples of manganese scavengers include phosphorus-containing compounds, organobromide compounds, and tricarbonyl compounds.
Among the phosphorus compounds useful in the present compositions are both inorganic and organic compounds. Typical inorganic phosphorus compounds include phosphonitrilic dichloride, phosphorus sesquisulfide, and the like. Typical organic compounds include the trivalent esters of phosphorus such as triphenyl phosphite, triethyl phosphite, diethyl phosphite, trimethyl phosphite, tri-secoctyl phosphite, tri(fi-chloroethylphosphite, and the like.
Another suitable class includes the pentavalent esters of phosphorus acids. Examples of these both in the alkyl and aryl categories include trimethyl phosphate, trimethyl thionophosphate, triethyl phosphate, tributyl phosphate, triisoamyl phosphate, dimethylphenyl phosphate, tri(β-chloropropyl)thionophosphate, tricresyl phosphate, dimethyl monoxylo phosphate, etc. Dimethyl monoaryl phosphates such as dimethyl phenyl phosphate may also be used.
Among the phosphorus compounds containing carbon-to-phosphorus bonds, the phosphines such as trimethyl phosphine, triethyl phosphine, trioctyl phosphine, triphenyl phosphine and the like may be used. Tertiary phosphine oxides such as trimethyl phosphine oxide, tripropyl phosphine oxide, triphenyl phosphine oxide and analogous phosphine sulfides such as triisobutyl phosphine sulfide and tribenzyl phosphine sulfide are also useful. Another class of suitable phosphorus compounds include the phosphonates such as diethyl methane phosphonate, diethyl propane phosphonate, dibutyl isoprene phosphonate, etc.
Various more complex phosphorus compounds such as the P2S5-active hydrogen compound reaction products, can also be employed, as can nitrogen-containing compounds such as aminophosphates, amidophosphites and sulfur analogs thereof.
Still further phosphorus compounds including the following:
or a tribologically acceptable salt thereof,
each R1 is the same or different and is independently selected from alkyl, alkenyl, cycloalkyl, cycloalkylalkyl, aryl, and aralkyl, wherein said aryl and aralkyl are optionally substituted with one to three substituents each independently selected from alkyl and alkenyl;
each R2 is independently selected from alkyl, alkenyl, cycloalkyl and cycloalkylalkyl;
Y is selected from the group consisting of alkyl, alkoxyalkyl, benzyl, and —R4—R5—R6;
R4 is alkylene;
R5 is selected from the group consisting of a bond, alkylene; —C(O)— and —C(R7)—;
R6 is selected from the group consisting of alkyl, hydroxyalkyl, hydroxyalkyleneoxy, hydroxy and alkoxy;
R7 is hydroxy;
X2 is selected from the group consisting of R8,
R8 is alkyl, alkenyl, cycloalkyl, cycloalkylalkyl, aryl, and aralkyl, wherein said aryl and aralkyl are optionally substituted with one to three substituents each independently selected from alkyl and alkenyl; and
Z is
The amount of phosphorus-containing compounds to be added can be varied. As a manganese scavenger, the amount of elemental phosphorus will correlate by some effective stoichiometric ratio with the amount of manganese in the additive or fully formulated fuel composition. This stoichiometric ratio of Mn:P may be from about 1:0.1 to 1:10, or alternatively 1:0.5 to 1:3.
It is also possible, and perhaps expected, that two or more phosphorus-containing compounds may be used. The different compounds may have different scavenging efficiencies. Different manganese-containing compounds may react differently with the different phosphorus compounds. Additionally, different phosphorus-containing compounds may have differing impacts on the rating number octane or other performance characteristics of an aviation fuel. Combinations of a plurality of phosphorus compounds may therefore be chosen to respond to the balance of their effects in the aviation fuel composition.
The organobromide scavenger compounds that may be used include the following: an organobromide compound selected from the group consisting of 1,2-dibromoethane; 3,5-dibromotoluene; 2,5-dibromotoluene; and 2,6-dibromo-4-methylaniline. Other possible organobromides are aryl organobromides, including but not limited to, substituted aryl bromides where the substituted group is between 1-5 substituents and can be an amine, alkyl group, aryl group, halide other than bromine, additional nitrogen containing groups, and phosphorous containing groups. Aromatic groups are not limited to benzene. For example naphthalene and other rings that meet the criteria for aromaticity may be used. This includes heteroaryl rings that contain nitrogen, oxygen, or sulfur. Alkyl organobromides (for instance, 1,2-dibromoethane) having an alkyl size of 1-15 carbons are also possible. Alkyl bromides can be straight chain, branched, or contain aromatic and cycloalkyl ring structures. They can also contain other elements such as nitrogen, phosphorous, oxygen, and sulfur.
The amount of organobromide scavenger compound will be proportional to the amount of manganese in the fuel additive or finished fuel composition. The amount may range from the stoichiometric ratio of Mn:Br of about 1:0.1 to 1:20, or alternatively, about 1:4 to 1:8.
Different organobromides may be used as determined by their effectiveness with a given manganese compound. Also, combinations of organobromides may be used.
The tricarbonyl scavenger compounds that may be used include the following: a tricarbonyl selected from the group consisting of glycerol triacetate; triethyl 1,1,2-ethanetricarboxylate; triethyl citrate, and tributyl citrate. Other possible tricarbonyls include a tricarbonyl selected from the group consisting of glycerol triacetate; triethyl 1,1,2-ethanetricarboxylate; triethyl citrate, and tributyl citrate. Other possible tricarbonyls include compounds that contain ethyl or linear propyl backbones as well as three carbonyl groups. The carbonyl groups can be directly bonded to the backbone as in triethyl 1,1,2-ethanetricarboxylate or separated by a spacer atom such as oxygen, sulfur, nitrogen, or phosphorous atom, for example glycerol triacetate. Further substituents, either singly or in combination, can be attached to the backbone including: alkyl, cycloalkyl, alkenyl, alkynyl, or aryl groups. Additionally groups containing elements such as oxygen, nitrogen, sulfur, chlorine, fluorine, bromine, and phosphorous can be attached to the backbone as in the cases of triethyl and tributyl citrate. The identity of the carbonyl group is typically an ester but can be a thioester, ketone, amide, or aldehyde. Substituents on the carbonyl group can be alkyl, cycloalky, alkenyl, alkynyl, or aryl groups. These substituents can contain heteroatoms such as oxygen, nitrogen, sulfur, chlorine, fluorine, bromine, and phosphorous. Functional groups that limit the storage stability, reduce scavenger solubility in fuel, or make the compound excessively or insufficiently volatile are disfavored.
The amount of tricarbonyl scavenger compound will be proportional to the amount of manganese in the fuel additive or finished fuel composition. The amount may range from 1:0.05 to 1:10 mass ratio of Mn to tricarbonyl. In particular a 1:0.5 to 1:3 mass ratio of Mn to scavenger may be used.
Different tricarbonyls and combinations of two or more tricarbonyls may be used as determined by their overall effectiveness with a given manganese compound and overall fuel composition.
In addition to each singular class of manganese scavengers, it is possible and intended that different scavengers from different classes of compounds may be used. In other words, one or more phosphorus-containing compounds may be combined and used with one or more organobromide compounds; one or more phosphorus-containing compounds may be combined and used with one or more tricarbonyl compounds; one or more tricarbonyl compounds may be used with one or more organobromide compounds; or, one or more phosphorus-containing compounds, one or more organobromide compounds, and one or more tricarbonyl compounds may all be combined and used together.
Structure of Scavenger Impacts ΔMON (Phosphorus-Containing Compound)
There are many benefits associated with the use of a scavenger when a manganese-containing additive is used with aviation fuel formulations. However, phosphorus-containing scavengers may impact the motor octane number (MON) when employed with a fuel formulation.
SAR Map of Phosphorous Scavengers
In order to explain the different effects on motor octane number with respect to different phosphorus-containing scavenger compounds, conclusions can be theorized based on the examples of phosphorus-containing scavenger as shown as
Tricarbonyl Scavenger Testing
To different tricarbonyl scavenger compounds were tested as compared with a base fuel and a fuel additized with a manganese-containing compound. Based on the table of
Tricarbonyl Scavenger Testing
The specific effects and benefits from the use of a tricarbonyl scavenger in the context of spark plug deposits as shown in
As shown, a reduction in engine deposits is a positive result when employing a scavenger as described herein. In addition to reducing deposits, those deposits may also be modified. For instance, instead of manganese oxide engine deposits, those deposits may instead be manganese phosphate or other manganese compounds that are less harmful. For instance, these alternative compounds may form and better able to be blown out of the engine during operation rather than growing deposits on the engine during operation.
These specific engine deposits that are reduced and/or modified include manganese-containing deposits formed on engine components such as spark plugs, intake valves, exhaust valves, and combustion chambers. These different locations of deposits may affect engine operation differently. It is believed that the reduction and/or modification of deposits using a scavenger as described herein is able to improve performance for liability of the engine overall.
Other embodiments of the present disclosure will be apparent to those skilled in the art from consideration of the specification and practice of the disclosure disclosed herein. As used throughout the specification and claims, “a” and/or “an” may refer to one or more than one. Unless otherwise indicated, all numbers expressing quantities of ingredients, properties such as molecular weight, percent, ratio, reaction conditions, and so forth used in the specification and claims are to be understood as being modified in all instances by the term “about.” Accordingly, unless indicated to the contrary, the numerical parameters set forth in the specification and claims are approximations that may vary depending upon the desired properties sought to be obtained by the present disclosure. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the disclosure are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the disclosure being indicated by the following claims.
| Number | Name | Date | Kind |
|---|---|---|---|
| 2399805 | Hurley et al. | May 1946 | A |
| 2479902 | Callingaert et al. | Aug 1949 | A |
| 2797153 | Bereslavsky | Jun 1957 | A |
| 2818417 | Brown et al. | Dec 1957 | A |
| 2860958 | Gilbert | Nov 1958 | A |
| 2889212 | Yust et al. | Jun 1959 | A |
| 2911431 | Orloff et al. | Nov 1959 | A |
| 3013039 | Lambert | Dec 1961 | A |
| 3023092 | Hook et al. | Feb 1962 | A |
| 3030009 | Neidhardt et al. | Apr 1962 | A |
| 3030396 | Gorsich | Apr 1962 | A |
| 3034877 | Popkin | May 1962 | A |
| 3037038 | Johnston et al. | May 1962 | A |
| 3038791 | Orloff et al. | Jun 1962 | A |
| 3042699 | Dayton | Jul 1962 | A |
| 3052528 | Roddick et al. | Sep 1962 | A |
| 3054740 | Schroll | Sep 1962 | A |
| 3055925 | Hartle | Sep 1962 | A |
| 3056667 | Payne et al. | Oct 1962 | A |
| 3060009 | Hook et al. | Oct 1962 | A |
| 3063819 | Watt et al. | Nov 1962 | A |
| 3065742 | Kawahara et al. | Nov 1962 | A |
| 3070430 | Lovett et al. | Dec 1962 | A |
| 3088814 | Gorsich et al. | May 1963 | A |
| 3092646 | Wilkinson | Jun 1963 | A |
| 3113005 | Gilbert | Dec 1963 | A |
| 3127351 | Brown et al. | Mar 1964 | A |
| 3130215 | Schroll | Apr 1964 | A |
| 3160592 | Brown | Dec 1964 | A |
| 3372200 | Stern, Jr. et al. | Mar 1968 | A |
| 3418091 | Barusch et al. | Dec 1968 | A |
| 3442361 | Gluckstein | May 1969 | A |
| 3522023 | Norton | Jul 1970 | A |
| 3558292 | Abowd | Jan 1971 | A |
| 3560174 | Newman et al. | Feb 1971 | A |
| 3615293 | Hnizda | Oct 1971 | A |
| 3658497 | Sung et al. | Apr 1972 | A |
| 3966429 | Sprague et al. | Jun 1976 | A |
| 4005993 | Niebylski et al. | Feb 1977 | A |
| 4390345 | Somorjai | Jun 1983 | A |
| 4720288 | Croudace et al. | Jan 1988 | A |
| 5470358 | Gaughan | Nov 1995 | A |
| 5511517 | Perry et al. | Apr 1996 | A |
| 5851241 | Studzinski et al. | Dec 1998 | A |
| 5944858 | Wallace | Aug 1999 | A |
| 6187064 | Henderson | Feb 2001 | B1 |
| 6238446 | Henderson | May 2001 | B1 |
| 6258134 | Studzinski et al. | Jul 2001 | B1 |
| 6451075 | Schoppe et al. | Sep 2002 | B1 |
| 6652608 | Orr | Nov 2003 | B1 |
| 7572303 | Orr | Aug 2009 | B2 |
| 7740668 | Gaughan et al. | Jun 2010 | B2 |
| 7775166 | Aradi et al. | Aug 2010 | B2 |
| 7833295 | Clark | Nov 2010 | B2 |
| 7897034 | De Oliviera et al. | Mar 2011 | B2 |
| 8016897 | Lowery | Sep 2011 | B2 |
| 8232437 | Clark et al. | Jul 2012 | B2 |
| 8628594 | Braly | Jan 2014 | B1 |
| 8734540 | Shea et al. | May 2014 | B2 |
| 9127225 | Shea et al. | Sep 2015 | B2 |
| 20020005008 | Studzinski | Jan 2002 | A1 |
| 20020045785 | Bazzani et al. | Apr 2002 | A1 |
| 20030040650 | Butler et al. | Feb 2003 | A1 |
| 20040124122 | Clark | Jul 2004 | A1 |
| 20050044778 | Orr | Mar 2005 | A1 |
| 20050188606 | Caprotti | Sep 2005 | A1 |
| 20060123696 | Gaughan et al. | Jun 2006 | A1 |
| 20060219096 | Aradi et al. | Oct 2006 | A1 |
| 20080000148 | Cunningham | Jan 2008 | A1 |
| 20080005958 | Factor | Jan 2008 | A1 |
| 20080244963 | Demoment et al. | Oct 2008 | A1 |
| 20100107480 | Lowry | May 2010 | A1 |
| 20100263262 | Gaughan | Oct 2010 | A1 |
| 20110114536 | Demoment | May 2011 | A1 |
| 20120000115 | Shastri | Jan 2012 | A1 |
| 20120029251 | Hemighaus et al. | Feb 2012 | A1 |
| 20130111805 | Mathur et al. | May 2013 | A1 |
| 20140116367 | Braly | May 2014 | A1 |
| 20140123548 | Braly | May 2014 | A1 |
| 20140128644 | Braly | May 2014 | A1 |
| 20150113861 | Shea et al. | Apr 2015 | A1 |
| 20150113862 | Shea et al. | Apr 2015 | A1 |
| 20150113866 | Shea et al. | Apr 2015 | A1 |
| 20150175920 | Shea et al. | Jun 2015 | A1 |
| 20150175921 | Shea et al. | Jun 2015 | A1 |
| 20150259616 | Albuzat et al. | Sep 2015 | A1 |
| Number | Date | Country |
|---|---|---|
| 732980 | Mar 2002 | AU |
| 2003252892 | Nov 2003 | AU |
| 2005201102 | Apr 2005 | AU |
| 2310056 | Dec 1999 | CA |
| 2256042 | Jul 2006 | CA |
| 0609089 | Aug 1994 | EP |
| 0910617 | Jul 2003 | EP |
| 1162768 | Sep 1958 | FR |
| 708006 | Apr 1954 | GB |
| 872820 | Jul 1961 | GB |
| 898343 | Jun 1962 | GB |
| 900446 | Jul 1962 | GB |
| 936364 | Sep 1963 | GB |
| 946062 | Jan 1964 | GB |
| 969913 | Sep 1964 | GB |
| 1343907 | Jan 1974 | GB |
| 2248068 | Mar 1992 | GB |
| 3660357 | Jun 2005 | JP |
| 2005272850 | Oct 2005 | JP |
| 2314334 | Jan 2008 | RU |
| 9640844 | Dec 1996 | WO |
| 9826028 | Jun 1998 | WO |
| 0222766 | Mar 2002 | WO |
| 2005087901 | Sep 2005 | WO |
| 2012015506 | Feb 2012 | WO |
| 2015197855 | Dec 2015 | WO |
| 2016010966 | Jan 2016 | WO |
| 2017123314 | Jul 2017 | WO |
| Entry |
|---|
| Examination Report No. 1 for corresponding AU Application No. AU 2017201950 dated Sep. 11, 2017. |
| Examination Report No. 1 for corresponding AU Application No. AU 2017201887 dated Sep. 11, 2017. |
| European Search Report, European Application No. 17161575.0, dated Jul. 10, 2017, 8 pages. |
| Thomas A. Ward, 3.4.1 Aviation Fuel, Aerospace Propulsion Systems, Jan. 1, 2010, pp. 202-213, 13 pages. |
| Partial European Search Report, European Application No. EP 17161582.6, dated Jun. 9, 2017, 15 pages. |
| Gunderloy F.C., Neblett R.F.; Effect of Phosphorous Deposit Modifiers on Gasoline Octane Quality. Journal of Chemical and Engineering Data. 1963, vol. 7, No. 1; pp. 142-145; 4 pages. |
| International Application Serial No. PCT/US/16/60749; Notification of Transmittial of the International Search Report and the Written Opinion of the International Searching Authority; 16 pages, dated Jan. 13, 2017. |
| Livingston H.K.; Antiknock Antogonists. Industrial and Engineering Chemistry. 1951, vol. 43 No. 3; pp. 663-671; 9 pages. |
| Number | Date | Country | |
|---|---|---|---|
| 20170283728 A1 | Oct 2017 | US |
