CA2080193C - Unleaded aviation gasoline - Google Patents

Unleaded aviation gasoline Download PDF

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CA2080193C
CA2080193C CA 2080193 CA2080193A CA2080193C CA 2080193 C CA2080193 C CA 2080193C CA 2080193 CA2080193 CA 2080193 CA 2080193 A CA2080193 A CA 2080193A CA 2080193 C CA2080193 C CA 2080193C
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CA2080193A1 (en
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Douglas Harold Henderson
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Afton Chemical Corp
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00Use of additives to fuels or fires for particular purposes
    • C10L10/10Use of additives to fuels or fires for particular purposes for improving the octane number
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/30Organic compounds compounds not mentioned before (complexes)
    • C10L1/305Organic compounds compounds not mentioned before (complexes) organo-metallic compounds (containing a metal to carbon bond)
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00Use of additives to fuels or fires for particular purposes
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/18Organic compounds containing oxygen
    • C10L1/182Organic compounds containing oxygen containing hydroxy groups; Salts thereof
    • C10L1/1822Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms
    • C10L1/1824Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms mono-hydroxy
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/18Organic compounds containing oxygen
    • C10L1/182Organic compounds containing oxygen containing hydroxy groups; Salts thereof
    • C10L1/183Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom
    • C10L1/1832Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom mono-hydroxy
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/18Organic compounds containing oxygen
    • C10L1/185Ethers; Acetals; Ketals; Aldehydes; Ketones
    • C10L1/1852Ethers; Acetals; Ketals; Orthoesters
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/22Organic compounds containing nitrogen
    • C10L1/222Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • C10L1/223Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond having at least one amino group bound to an aromatic carbon atom
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/22Organic compounds containing nitrogen
    • C10L1/226Organic compounds containing nitrogen containing at least one nitrogen-to-nitrogen bond, e.g. azo compounds, azides, hydrazines

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Lubricants (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

An unleaded aviation gasoline composition which comprises a blend of hydrocarbons and at least one cyclopentadienyl manganese tricarbonyl compound dissolved therein in an amount such that the composition has a minimum knock value lean rating octane number of 100 as determined by ASTM Test Method D2700 and wherein Motor Method octane ratings are converted to aviation ratings in the man-ner described in ASTM Specification D910-90, the composition being further characterized by having: a) a distillation temperature by ASTM Test Method D86 of 10% evaporated, 167°F maximum temperature;
40% evaporated, 167°F maximum temperature; 90% evaporated, 275°F
maximum temperature; and a final boiling point of 338°F maximum temperature; the sum of the 10 and 50% evaporated temperatures being 307°F minimum; the distillation recovery being 97% minimum;
the distillation residue being 1.5% maximum; and the distillation loss being 1.5% maximum; b) a heat of combustion by ASTM Test Method D1405 and as calculated from Table 1 thereof of 18,720 btu per pound minimum, or a heat of combustion by ASTM Test Method D2382 of 18,700 btu per pound minimum, the latter method controlling in case of a discrepancy therebetween; c) a vapor pressure by ASTM Test Method D323 or D2551 of 5.5 psi minimum and 7.0 psi maximum; d) a copper strip corrosion by ASTM Test Method D130 of number 1, maximum; e) a potential gum (5-hour aging gum) by ASTM Test Method D873 of 6 mg per 100 mL maximum, or a potential gum (16-hour aging gum by ASTM Test Method D873) of 10 mg per 100 mL; f) a sulfur content by ASTM Test Method D1266 or D2622 of 0.05% by weight maximum; g) a freezing point by ASTM Test Method D2386 of -72°F maximum; and h) a Water reaction by ASTM Test Method D1094 wherein the volume change, if any, does not exceed ~
2 mL.

Description

Patent 2C~~193 Case EI-6446 JFS:km UNLEADED AVIATION GASOLINE
This invention relates to unleaded aviation gasoline compositions which satisfy the specification requirements of ASTM
Specification D910-90.
The specifications imposed upon aviation gasolines are necessarily extremely rigorous. Use of an off-specification motor gasoline in a passenger car or truck can, at worse, result in poor engine performance, stalling, or other operational problem which, while annoying, are normally not life-threatening. In contrast, if an aviation gasoline does not perform properly in a spark-ignition aviation engine, the consequences could be disastrous.
While leaded aviation gasolines have performed wonderfully well in actual service for many years*, many misguided persons have clamored for elimination of lead from gasoline. If their efforts succeed, the refining industry will be faced with the problem of trying to provide unleaded aviation gasoline that performs as well as leaded aviation gasoline and that does not exceed the economic constraints of the marketplace.
This invention is deemed to overcome the above problem most expeditiously.
In accordance with this invention, there is provided an unleaded aviation gasoline composition which comprises a blend of hydrocarbons and at least one cyclopentadienyl manganese tricar-bonyl compound dissolved therein in an amount such that said gaso-line composition has a minimum knock value lean rating octane num-ber of 100 as determined by ASTM Test Method D2700 and wherein Motor Method octane ratings are converted to aviation ratings in the manner described in ASTM Specification D910-90, said composition being further characterized by having: a) a distillation temperature as determined by ASTM Test Method D86 of 10% evaporated, 167°F maximum temperature; 40o evaporated, 167°F
maximum temperature; 90% evaporated, 275°F maximum temperature; and a final boiling point of * It may well be remembered that leaded aviation gaso3ine was deemed at least partially responsible for the successful Battle of Britain.

338°F maximum temperature; the sum of the 10 and 50% evaporated temperatures being 307°F minimum; the distillation recovery being 97% minimum; the distillation residue being 1.5% maximum; and the distillation loss being 1.5o maximum; b) a heat of combustion as determined by ASTM Test Method D1405 and as calculated from Table 1 thereof of 18,720 btu per pound minimum, or a heat of combustion as determined by ASTM Test Method D2 3 82 of 18 , 7 00 btu per pound minimum, the latter method controlling in case of a discrepancy therebetween; c) a vapor pressure as determined by ASTM Test Method D323 or D2551 of 5.5 psi minimum and 7.0 psi maximum; d) a copper strip corrosion as determined by ASTM Test Method D130 of number 1, maximum; e) a potential gum (5-hour aging gum) as de-termined by ASTM Test Method D873 of 6 mg per 100 mL maximum, or a potential gum (16-hour aging gum as determined by ASTM Test Method D873) of 10 mg per 100 mL; f) a sulfur content as determined by ASTM Test Method D1266 or D2622 of 0.05% by weight maximum; g) a freezing point as determined by ASTM Test Method D2386 of -72°F
maximum; and h) a water reaction as determined by ASTM Test Method D1094 wherein the volume change, if any, does not exceed ~ 2 mL.
Preferred gasoline compositions are those in which the gaso line composition additionally has a minimum performance number re ported to the nearest whole number and as determined by ASTM Test Method D909 of 130. In this connection, a minimum performance num ber of 130 is equivalent to a knock value determined using isooc tane plus 1.28 milliliters of tetraethyllead per gallon.
Another embodiment of this invention provides the method of operating a four stroke cycle, reciprocating piston aircraft engine which comprises providing or using as the fuel for said engine a gasoline composition of this invention.
Still another embodiment of this invention provides, in combination, at least one four stroke cycle, reciprocating piston aircraft engine and at least one fuel storage tank operatively connected with said at least one engine so as to deliver fuel required to operate said engine, said at least one fuel storage tank containing a gasoline composition of this invention as the fuel for said engine.
Cyclopentadienyl manganese tricarbonyl compounds which can be used in the practice of this invention include cyclopentadienyl manganese tricarbonyl, methylcyclopentadienyl manganese. tricar-bonyl, dimethylcyclopentadienyl manganese tricarbonyl, trimethylcy-clopentadienyl manganese tricarbonyl, tetramethylcyclopentadienyl i manganese tricarbonyl, pentamethylcyclopentadienyl manganese tri-carbonyl, ethylcyclopentadienyl manganese tricarbonyl, diethylcy-clopentadienyl manganese tricarbonyl, propylcyclopentadienyl manga-nese tricarbonyl, isopropylcyclopentadienyl manganese tricarbonyl, tert-butylcyclopentadienyl manganese tricarbonyl, octylcyclopen-tadienyl manganese tricarbonyl, dodecylcyclopentadienyl manganese tricarbonyl, ethylmethylcyclopentadienyl manganese tricarbonyl, in-denyl manganese tricarbonyl, and the like, including mixtures of two or more such compounds. Preferred are the cyclopentadienyl l0 manganese tricarbonyls which are liquid at room temperature such as methylcyclopentadienylmanganese tricarbonyl,ethylcyclopentadienyl manganese tricarbonyl, liquid mixtures of cyclopentadienyl man-ganese tricarbonyl and methylcyclopentadienyl manganese tricar-bonyl, mixtures of methylcyclopentadienyl manganese tricarbonyl and ethylcyclopentadienyl manganese tricarbonyl, etc. Preparation of such compounds is described in the literature, for example, U.S.
2,818,417.
In another preferred embodiment the unleaded gasoline compo-sition additionally contains at least one antioxidant in an amount 2o not in excess of 8.4 pounds per 1000 barrels, said antioxidant being selected from the group N,N'-diisopropyl-p-phenylenediamine, N,N'-di-sec-butyl-p-phenylenediamine, 2,4-dimethyl-6-tert-butylphe-nol, 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butylphenol, a mixture of 75% minimum 2,6-di-tert-butylphenol plus 25% maximum di-and tri-tent-butylphenol; and a mixture of 75% minimum di- and tri-isopropyl phenols plus 25% maximum di- and tri-tert-butylphenol.
Most preferably the amount of such antioxidant does not exceed 4.2 pounds per 1000 barrels.
It is to be understood that the fuels of this invention 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 practice of this inven-tion.
The base fuels used in the foregoing compositions can be blends of refined hydrocarbon derived from crude petroleum, natural gasoline, or blends thereof with synthetic hydrocarbons or aromatic hydrocarbons, yr both. Blending components, if approved for use in aviation gasolines, such as oxygenated ingredients or the like, can be included. Rarely, if ever, will the content of aromatic hydro-carbons in the gasoline exceed levels above 25%. As noted above, L., Ci vJ.JLJ a.) the overall composition must satisfy the requirements a) through h) inclusive as set forth above.
Other components which can be employed, and under certain cir-cumstances are preferably employed, include dyes which do not con-s tribute to excessive induction system deposits. Typical dyes which can be employed are 1,4-dialkylaminoanthraquinone, p-diethylamino-azobenzene (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 azoben-zene-4-azo-2-naphthol, or equivalent materials. The amounts used should, wherever possible, conform to the limits specified in ASTM
Specification D910-90.
Fuel system icing inhibitors may also be included in the fuels of this invention. Preferred are ethylene glycol monomethyl ether and isopropyl alcohol, although materials giving equivalent perfor-mance may be considered acceptable for use. Amounts used should, wherever possible, conform to the limits referred to in ASTM
Specification D910-90.
The concentration of the cyclopentadienyl manganese tricarbo-nyl compound used in the unleaded aviation gasoline base stock satisfying the above criteria will vary to some extent depending upon the identity and properties of the base fuel and the octane quality desired in the finished fuel. Ordinarily amounts equiva-lent to 0.01 to about 0.5 gram of manganese per gallon of fuel are sufficient, although higher amounts can be used whenever deemed necessary or appropriate, provided that the resultant fuel compo sition satisfies the requirements of a) through h) above. Prefera bly the fuel will contain up to about 0.25 gram of manganese per gallon as one or more cyclopentadienyl manganese tricarbonyl com pounds.
There are good and sufficient reasons why the gasoline compo-sition is to comply with the requirements set forth above as a) through h). The rationale behind these requirements as set forth in ASTM Specification D910-90 are as follows:
"X1.1.1. Aviation gasoline is a complex mixture of relatively volatile hydrocarbons that vary widely in their physical and chemical properties. The engines and aircraft impose a variety of mechanical, physical, and chemical environments.
The properties of aviation gasoline ... must be -properly balanced to give satisfactory engine performance over an extremely wide range of conditions.
2~~~~.93 Y1.1.3. Specifications covering antiknock quality define the grades of aviation gasoline. The other requirements either prescribe the proper balance of properties to ensure satisfac-tory engine performance or limit components of undesirable nature to concentrations so low that they will not have an adverse effect on engine performance.
X1.2.1. The fuel-air mixture in the cylinder of a spark-ignition engine will, under certain conditions, ignite spon-taneously in localized areas instead of progressing from the spark. This may cause a detonation or knock, usually inaudible in aircraft engines. This knock, if permitted to continue for more than brief periods, may result in serious loss of power and damage to or destruction of the aircraft engine. When aviation gasoline is used in other types of aviation engines, far example, in certain turbine engines where specifically permitted by the engine manufacturers, knock or detonation characteristics may not be critical requirements."
In accordance with other preferred embodiments this invention further provides:

A) The method of operating a four stroke cycle, reciprocating piston aircraft engine which comprises providing and/or using as the fuel for said engine a gasoline composition of this invention, and providing and/or using as the lubricating oil for said engine a lubricating oil composition satisfying the chemical and physical property requirements set forth below;

and B) Apparatus which comprises in combination (i) at least one four stroke cycle, reciprocating piston aircraft engine, (ii) at least one fuel storage tank operatively connected with said at least one engine so as to deliver fuel required to operate said engine, and (iii) at least one chamber in said engine for receiving and maintaining a supply of lubricating oil for lubricating said engine during operation thereof, said at least one fuel storage tank containing a gasoline composition of this invention as the fuel for said engine and said at least one chamber containing as the lubricating oil for said engine a lubricating oil composition satisfying the chemical and physical property requirements set forth below.

The chemical and physical property requirements of the lubricating oil used In the foregoing preferred embodiments A) and B) are as follows:

~C~~~193 1) Viscosity, cSt, per ASTM D 445:
SAE Grade Minimum at 100°C Less than at 100°C
30 9.3 12.5 40 12.5 16.3 50 16.3 21.9 60 21.9 26.1 2) Multigrade oil shall meet the viscosity requirements and the Low Temperature Viscosity Cold Crank Simulation requirements of SAE Test Method J300 for the designated grade.
3) Viscosity Index, minimum per ASTM D 2270: 100 for SAE grades 30, 40 and Multigrade; 95 for SAE grades 50 and 60.
4) Flash Point, °C, minimum per ASTM D 92: 220 for SAE grades 30 and Multigrade; 225 for SAE grade 40; and 243 for SAE grades 50 and 60.
5) Pour Point, C, maximum per ASTM D 97: -24 for SAE grade 30;

-22 for SAE grade 40; and -18 for SAE grades 50 and 60.
6) Viscosity, High Temperature, High Shear at 150C, cP, minimum per ASTM D 4683, D 4741, D 4624: 3.3 for all viscosity grades.
7) Total Acid Number, mg KOH/g, maximum (titrated to a pH 11 end point) per ASTM D 664: 1.0 for all viscosity grades.
8) Ash Content, Mass o, maximum per ASTM D 482: 0.006 for all viscosity grades.
9) Trace Sediment, mL/100 mL Oil, maximum per ASTM D 2273: 0.005 for all viscosity grades.
10) Copper Strip Corrosion, maximum rating per ASTM D 130: I

after 3 hours @ 100C for all viscosity grades; and 3 after hours @ 204C for all viscosity grades.
11) Foaming Tendency/Stability per ASTM D 892: Aerated Volume, mL, maximum for all viscosity grades per Sequences I, II and III: 50; Volume after 10 minutes, mL, maximum for all viscosity grades per Sequences 1, II, and III: 0.
12) Compatibility with other oils per FTM 791 Method 3403: All viscosity grades shall pass.
13) Elastomer Compatibility, % swelling, acceptable range for all viscosity grades after 72 hours per FTM 791 Method 3604 (except conducted with the specific materials and temperatures herein listed):
Material Test Temperature Acceptable Limits AMS-3217/1 70C (158F) ' 5 to + 5 AMS-3217/4 150C (302F) - 5 to + 5 AMS-3217/5 150C (302'F) - 5 to + 5 US Navy Silicone Rubber 121C (250F) 0 to + 20 ~~~ ~ ~~.'~3 14) Trace Metal Content, ppm, maximum for all viscosity grades, per test method of Paragraph 4.5.2 of MIL-L-22851D (1 December 1990) or equivalent: Iron, 5; Silver, 3; Aluminum, 7;
Chromium, 5; Copper, 3; Magnesium, ~; Nickel, 3; Lead, 5;
Silicon, 25; Tin, 10: Titanium, 2; Molybdenum, 4.
The most preferred lubricating oils will not only meet the above requirements 1) through 14) but in addition, will meet the following L-38 Engine Test Requirements:
15) Total Bearing Weight Loss, mg, maximum per ASTM STP 509A, Part IV for all viscosity grades: 500.
16 ) Used Oil Viscosity, Stripped, maximum % Change @ 40 ° C per ASTM
D 445 for all single viscosity grades: -15 to + 10.
17) Used Oil Viscosity at 100°C of Multi-grade Oil per SAE J300 shall remain in SAE J300 grade.
18) Used Oil Total Acid Number, maximum change for all viscosity grades per ASTM D 664 (titrated to a pH 11 end point): 2Ø
This invention is susceptible to considerable variation. Thus it is not intended that this invention be limited by the specific exemplifications set forth hereinabove. Rather what is intended to be covered is the subject matter within the spirit and scope of the ensuing claims.
_ 7 _

Claims (14)

1. An unleaded aviation gasoline composition which comprises a blend of hydrocarbons and at least one cyclopentadienyl manganese tricarbonyl compound dissolved therein in an amount ranging between about 0.01 and about 0.5 grams of manganese per gallon of fuel such that said gasoline composition has a minimum knock value lean rating octane number of 100 as determined by ASTM
Test Method D2700 and wherein Motor Method octane ratings are converted to aviation ratings in the manner described in ASTM
Specification D910-90, said composition being further characterized by having:
a) a distillation temperature as determined by ASTM Test Method D86 of 10% evaporated, 167°F maximum temperature; 40%
evaporated, 167°F maximum temperature: 90% evaporated, 275°F
maximum temperature; and a final boiling point of 338°F
maximum temperature; the sum of the 10 and 50% evaporated temperatures being 307°F minimum; the distillation recovery being 97% minimum; the distillation residue being 1.5%
maximum; and the distillation loss being 1.5% maximum;
b) a heat of combustion as determined by ASTM Test Method D1405 and as calculated from Table 1 thereof of 18,720 btu per pound minimum, or a heat of combustion as determined by ASTM Test Method D2382 of 18,700 btu per pound minimum, the latter method controlling in case of a discrepancy therebetween;
c) a vapor pressure as determined by ASTM Test Method D323 or D2551 of 5.5 psi minimum and 7.0 psi maximum;
d) a copper strip corrosion as determined by ASTM Test Method D130 of number 1, maximum;
e) a potential gum (5-hour aging gum) as determined by ASTM Test Method D873 of 6 mg per 100 mL maximum, or a potential gum (16-hour aging gum as determined by ASTM Test Method D873) of 10 mg per 100 mL;
f) a sulfur content as determined by ASTM Test Method D1266 or D2622 of 0.05% by weight maximum;
g) a freezing point as determined by ASTM Test Method D2386 of -72°F maximum: and h) a water reaction as determined by ASTM Test Method D1094 wherein the volume change, if any, does not exceed ~ 2 mL.
2. A composition as claimed in Claim 1 wherein said gasoline composition has a minimum knock value lean rating octane number of 100 as determined by ASTM Test Method D2700 and a minimum perfor-mance number reported to the nearest whole number and as determined by ASTM Test Method D909 of 130.
3. A composition as claimed in Claim 1 wherein said cyclo-pentadienyl manganese tricarbonyl compound consists essentially of methylcyclopentadienyl manganese tricarbonyl.
4. A composition as claimed in Claim 1 wherein said composi-tion additionally contains at least one antioxidant in an amount not in excess of 8.4 pounds per 1000 barrels, said antioxidant being selected from the group N,N'-diisopropyl-p-phenylenediamine, N,N'-di-sec-butyl-p-phenylenediamine, 2,4-dimethyl-6-tert-butyl-phenol, 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butylphenol, a mixture of 75% minimum 2,6-di-tert-butylphenol plus 25% maximum di- and tri-tert-butylphenol; and a mixture of 75% minimum di- and triisopropyl phenols plus 25% maximum di- and tri-tert-butylphenol.
5. A composition as claimed in Claim 4 wherein the amount of said antioxidant is not in excess of 4.2 pounds per 1000 barrels.
6. The method of operating a four stroke cycle, reciprocating piston aircraft engine which comprises providing or using as the fuel for said engine an unleaded aviation gasoline composition which comprises a blend of hydrocarbons and at least one cyclopentadienyl manganese tricarbonyl compound dissolved therein in an amount ranging between about 0.01 and about 0.5 grams of manganese per gallon of fuel such that said gasoline composition has a minimum knock value lean rating octane number of 100 as determined by ASTM Test Method D2700 and wherein Motor Method octane ratings are converted to aviation ratings in the manner described in ASTM Specification D910-90, raid composition being further characterized by having:
a) a distillation temperature as determined by ASTM Test Method D86 of 10% evaporated, 167°F maximum temperature; 40%
evaporated, 167°F maximum temperature; 90% evaporated, 275°F
maximum temperature; and a final boiling point of 338°F
maximum temperature; the sum of the 10 and 50% evaporated temperatures being 307°F minimum; the distillation recovery being 97% minimum; the distillation residue being 1.5%
maximum; and the distillation loss being 1.5% maximum;
b) a heat of combustion as determined by ASTM Test Method D1405 and as calculated from Table 1 thereof of 18,720 btu per pound minimum, or a heat of combustion as determined by ASTM Test Method D2382 of 18,700 btu per pound minimum, the latter method controlling in case of a discrepancy therebetween;
c) a vapor pressure as determined by ASTM Test Method D323 or D2551 of 5.5 psi minimum and 7.0 psi maximum;
d) a copper strip corrosion as determined by ASTM Test Method D130 of number 1, maximum;

e) a potential gum (5-hour aging gum) as determined by ASTM Test Method D873 of 6 mg per 100 mL maximum, or a potential gum (16-hour aging gum as determined by ASTM Test Method D873) of 10 mg per 100 mL;
f) a sulfur content as determined by ASTM Test Method D1266 or D2622 of 0.05% by weight maximum;
g) a freezing point as determined by ASTM Test Method D2386 of -72°F maximum; and h) a water reaction as determined by ASTM Test Method D1094 wherein the volume change, if any, does not exceed ~ 2 mL.
7. A method as claimed in Claim 6 wherein said gasoline composition has a minimum knock value lean rating octane number of 100 as determined by ASTM Test Method D2700 and a minimum perfor-mance number reported to the nearest whole number and as determined by ASTM Test Method D909 of 130.
8. A method as claimed in Claim 6 wherein said cyclopenta-dienyl manganese tricarbonyl compound consists essentially of methylcyclopentadienyl manganese tricarbonyl.
9. A method as claimed in Claim 6 wherein said composition additionally contains at least one antioxidant in an amount not in excess of 8.4 pounds per 1000 barrels, said antioxidant being se-lected from the group N,N'-diisopropyl-p-phenylenediamine, N,N'-di-sec-butyl-p-phenylenediamine, 2,4-dimethyl-6-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butylphenol, a mixture of 75% minimum 2,6-di-tert-butylphenol plus 25% maximum di- and tri-tert-butylphenol; and a mixture of 75% minimum di- and triisopropyl phenols plus 25% maximum di- and tri-tert-butylphenol.
10. A composition as claimed in Claim 9 wherein the amount of said antioxidant is not in excess of 4.2 pounds per 1000 barrels.
11. The method of operating a four stroke cycle, reciprocating piston aircraft engine which comprises:
A) providing and/or using as the fuel for said engine an unleaded aviation gasoline composition which comprises a blend of hydrocarbons and at least one cyclopentadienyl manganese tricarbonyl compound dissolved therein in an amount ranging between about 0.01 and about 0.5 grams of manganese per gallon of fuel such that said gasoline composition has a minimum knock value lean rating octane number of 100 as determined by ASTM Test Method D2700 and wherein Motor Method octane ratings are converted to aviation ratings in the manner described in ASTM Specification D910-90, said composition being further characterized by having:
a) a distillation temperature as determined by ASTM Test Method D86 of 10% evaporated, 167°F maximum temperature; 40%
evaporated, 167°F maximum temperature; 90% evaporated, 275°F
maximum temperature; and a final boiling point of 338°F
maximum temperature; the sum of the 10 and 50% evaporated temperatures being 307°F minimum; the distillation recovery being 97% minimum; the distillation residue being 1.5%
maximum; and the distillation loss being 1.5% maximum;
b) a heat of combustion as determined by ASTM Test Method D1405 and as calculated from Table 1 thereof of 18,720 btu per pound minimum, or a heat of combustion as determined by ASTM Test Method D2382 of 18,700 btu per pound minimum, the latter method controlling in case of a discrepancy therebetween;
c) a vapor pressure as determined by ASTM Test Method D323 or D2551 of 5.5 psi minimum and 7.0 psi maximum;
d) a copper strip corrosion as determined by ASTM Test Method D130 of number 1, maximum;
e) a potential gum (5-hour aging gum) as determined by ASTM Test Method D873 of 6 mg per 100 mL maximum, or a potential gum (16-hour aging gum as determined by ASTM Test Method D873) of 10 mg per 100 mL;
f) a sulfur content as determined by ASTM Test Method D1266 or D2622 of 0.05% by weight maximum;
g) a freezing point as determined by ASTM Test Method D2386 of -72°F maximum; and h) a water reaction as determined by ASTM Test Method D1094 wherein the volume change, if any, does not exceed ~ 2 mL; and e) providing and/or using as the lubricating oil for said engine a lubricating oil composition satisfying the following chemical and physical property requirements:
1) Viscosity, cSt, per ASTM D 445:
SAE Grade ~Minimum at 100°C ~Less than at 100°C

30 ~~~9.3 ~~~~12.5 40 ~~~12.5 ~~~~16.3 50 ~~~16.3 ~~~~21.9 60 ~~~21.9 ~~~~26.1 2) Multigrade oil shall meet the viscosity requirements and the Low Temperature Viscosity Cold Crank Simulation requirements of SAE Test Method J300 for the designated grade.
3) Viscosity Index, minimum per ASTM D 2270: 100 for SAE grades 30, 40 and Multigrade; 95 for SAE grades 50 and 60.
4) Flash Point, °C, minimum per ASTM D 92: 220 for SAE grades 30 and Multigrade; 225 for SAE grade 40; and 243 for SAE grades 50 and 60.
5) Pour Point, °C, maximum per ASTM D 97: -24 for SAE grade 30;
-22 for SAE grade 40; and -18 for SAE grades 50 and 60.
6) Viscosity, High Temperature, High Shear at 150°C, cP, minimum per ASTM D 4683, D 4741, D 4624: 3.3 for all viscosity grades.
7) Total Acid Number, mg KOH/g, maximum (titrated to a pH 11 end point) per ASTM D 664: 1.0 for all viscosity grades.
8) Ash Content, Mass %, maximum per ASTM D 482: 0.006 for all viscosity grades.
9) Trace Sediment, mL/100 mL Oil, maximum per ASTM D 2273: 0.005 for all viscosity grades.
10) Copper Strip Corrosion, maximum rating per ASTM D 130: 1 after 3 hours @ 100°C for all viscosity grades; and 3 after 3 hours @ 204°C for all viscosity grades.
11) Foaming Tendency/Stability per ASTM D 892: Aerated Volume, mL, maximum for all viscosity grades per Sequences I, II and III: 50; Volume after 10 minutes, mL, maximum for all viscosity grades per Sequences 1, II, and III: 0.
12) Compatibility with other oils per FTM 791 Method 3403: All viscosity grades shall pass.
13) Elastomer Compatibility, % swelling, acceptable range for all viscosity grades after 72 hours per FTM 791 Method 3604 (except conducted with the specific materials and temperatures herein listed):

Material ~~ Test Temperature ~~Acceptable Limits AMS-3217/1 ~ 70°C (158°F) ~- 5 to + 5 AMS-3217/4 ~ 150°C (302°F) ~- 5 to + 5 AMS-3217/5 ~ 150°C (302°F)~- 5 to + 5 US Navy Silicone Rubber 121°C (250°F) ~ 0 to + 20
14) Trace Metal Content, ppm, maximum for all viscosity grades, per test method of Paragraph 4.5.2 of MIL-L-22851D (1 December 1990) or equivalent: Iron, 5; Silver, 3; Aluminum, 7; Chro-mium, 5; Copper, 3; Magnesium, 3; Nickel, 3; Lead, 5; Silicon, 25; Tin, 10; Titanium, 2; Molybdenum, 4.
CA 2080193 1991-10-28 1992-10-08 Unleaded aviation gasoline Expired - Lifetime CA2080193C (en)

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US6238446B1 (en) * 1991-10-28 2001-05-29 Ethyl Petroleum Additives, Inc. Unleaded aviation gasoline
US6652608B1 (en) 1994-03-02 2003-11-25 William C. Orr Fuel compositions exhibiting improved fuel stability
EP0748364B1 (en) * 1994-03-02 2007-11-21 ORR, William C. Unleaded fuel compositions
CA2194572A1 (en) * 1994-05-31 1995-12-07 William C. Orr Vapor phase combustion methods and compositions
US5509944A (en) * 1994-08-09 1996-04-23 Exxon Chemical Patents Inc. Stabilization of gasoline and gasoline mixtures
FR2933102B1 (en) 2008-06-30 2010-08-27 Total France AVIATION GASOLINE FOR AIRCRAFT PISTON ENGINES, PROCESS FOR PREPARING THE SAME

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FR2594138B1 (en) * 1986-02-11 1988-05-20 Inst Francais Du Petrole PROCESS FOR OBTAINING SUPERFUEL AND FUEL FOR A FUEL FROM CUT BUTANES AND / OR C4 CUTS FROM CRACKING OR CATALYTIC REFORMING
CA2045455C (en) * 1990-07-13 2002-04-02 John Vincent Hanlon Motor fuels of enhanced properties

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DE69215333D1 (en) 1997-01-02
AU2724992A (en) 1993-04-29
AU656237B2 (en) 1995-01-27
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DE69215333T2 (en) 1997-03-20
JPH05239477A (en) 1993-09-17
CA2080193A1 (en) 1993-04-29

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