Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS 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
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/30—Organic compounds compounds not mentioned before (complexes)

Definitions

• This invention is an improved liquid fuel of the gasoline type and additive therefor, for an internal combustion engine of the higher compression ratio range employing an electric spark for igniting the combustible fuel mixture, and an improved method of operating such an engine.
• the fuel is a blend of a conventional hydrocarbon motor fuel of appropriate boiling range and octane number, tetraethyl lead in the usual range of amounts, and a smaller amount of one or more compounds selected from the trialkyl phosphines, as described more fully below, with or without other additives.
• the trialkyl phosphines are a known but little used group of compounds. Their preparation is well enough known to need no description here.
• the general empirical formula is RsP, in which R is an alkyl group which need not be the same at all three positions in the molecule.
• the trialkyl phosphines which are useful for the present purpose are those in which the alkyl groups are in the range from methyl (CH3) to amyl (CsHn) inclusive, namely, C1 to C3 alkyl groups, primary and secondary C4 alkyl groups, and primary C5 alkyl groups.
• the preferred species are those in which at least two of the alkyl groups are in the range from C2 to C4.
• This preferred group thus includes, in addition to the compounds having the same alkyl group at all three positions, such compounds as diethyl methyl phosphine, diethyl propyl phosphine, diethyl isopropyl phosphine, the diethyl butyl phosphines, and the diethyl amyl phosphines.
• the predominant component or" the fuel blend is the hydrocarbon material which is a mixture of hydrocarbons boiling in the gasoline range from an initial of about 120 F. to a 90% point of about 400 F. or somewhat lower, and an end-point of about 440 F., all as measured by the A. S. T. M. distillation method. In the case of an aviation fuel, the 90% point and the end-point are lower, but within the range stated.
• the octane range in terms of Research octane number, is upwards of 85, and includes the range above 100 now identified primarily with fuel for aircraft spark-ignition engines and rated in terms of performance number.
• the octane value in addition to being increased by the tetraethyl lead additive, may be the result of special catalytic or pyrolytic conversion processing or of other additives such as alkylates or other hydrocarbons having a very high octane blending number. I refer to this major component of theblend as high octane gasoline.
• trialkyl phosphines are present in my blend in an amount which, by volume, ranges from about 0.2 cc. per gallon to about 1 cc. per gallon of hydrocarbon fuel. More than 1 cc./gal. can be used, but the excess is not economically justified in most cases. Essentially the same values represent also the proportion of the phosphine in the total blend. In percentage terms, the range is from about 0.005% to about 0.025%, by volume, of the blend. Within the stated range, smaller amounts of the lower alkyls, e. g., Cg, are needed than of 2,797153? Patented June 25, 1951 the higher alkyls. For the preferred examples, 0.3 cc. of triethyl phosphine correspond in effect to about 0.4 cc. of tripropyl phosphine and to about 0.5 cc. of tributyl phosphine.
• the engines in which the invention has its utility are those spark-ignition internal combustion engines in which the compression ratio is above 7.5 :1, recognized as the range of higher compression engines.
• the best results are obtained with engines having a compression ratio in the range of about 8.5 :1 and above. In present practice, the ratio ranges up to 10:1, and in the future it may go to 12:1.
• the utility of the invention is that such an engine, when supplied with the described fuel in admixture with air for combustion, suffers fewer deposit-induced or surface ignitions and produces less spark plug fouling than when operated with the same fuel without the trialkyl phosphine.
• the engine thus delivers more power, because of the reduced loss from abnormal combustion.
• my fuel requires a smaller weight of additive to achieve an acceptable reduction of abnormal combustion and, further, by causing thinner deposits in the combustion space, it minimizes the increase in the octane requirement of the engine caused by the deposits.
• chloropropyl thionophosphate usually called IQC. This is used in substantially the same amount, or slightly smaller amount, around 0.55 cc./gal. (0.70 gm./ gal.) with generally comparable results.
• my fuel is as effective in this respect as a commercial motor fuel having tricresyl phosphate, and it achieves the commercially acceptable degree of improvement with a materially smaller amount of additive.
• the volume ratio of 0.51 to 0.67 as given above corresponds to a weight ratio of 0.414.gm./gal. to 0.7926 gm./gal. .of fuel blend; and from the practical standpoint, since such materials are purchased by weight, the significant fact is that little more than half the weight of tributyl phosphine is needed to match the effect of the maximum commercially used quantity of tricresyl phosphate.
• the base fuel used as a control was a commercial premium grade gasoline having 3 cc./ gal. of TEL and a Research octane number of 92. It showed a count ,of 135.
• the same fuel with an addition of 0.55 cc./gal. (0.70 gm./gal.) of the additive known as ICC (chloropropyl thionophosphate) showed a count of 53, which is a distinct improvement with respect to abnormal combustion and an improvement representative of what is commercially acceptable, warranting use of the additive.
• My fuel tested in comparison with these, consisted of a commercial premium gasoline of 95 octane number -(Research) having 3 cc./gal. of TEL and 0.5 cc./gal. of tri-n-butyl phosphine.
• This same fuel without that addition of the phosphine was generally comparable with the base fuel of the ICC test, although somewhat higher in "octane number (95 vs. 92'), and is referred to below as the second base fuel of this series of tests. It showed a count of 140, which is typical of commercial premium gasolines having no additive to reduce abnormal combustion. In contrast, my fuel showed-a-count of only 47, as an average of four runs, evidencing a superior performance in reduction of abnormal combustion,
• My fuel while capable of achieving the commercially acceptable degree of reduction of abnormal combustion, does so with a smaller increase in total deposit and therefore with a lesser increase in octane requirement; and it does this with little more than half the weight of additive. It is believed that prolonged use of my fuel will also show the deposit to be of a less adherent nature, more readily removable, and that this characteristic of the deposit may be related to its effect of leaving a thinner deposit in that the engine purges itself of a greater part of the depositing or deposited material.
• trialkyl phosphines are readily miscible 'with tetraethyl lead fluid, that they are more soluble in hydrocarbon fuels than TCP and ICC, and that as a class they are more compatible with gasolines in specific gravity and boiling point.
• a single additive composed of tetraethyl lead and the trialkyl phosphine can be prepared, in inti- .mate mixture, with .or without a solvent carrier; and better distribution throughout the gasoline can thereby be obtained than when thephosphine is added alone.
• thetrialkyl phosphines range from about 0.8 to 0.815, where TCP and ICC have specific gravities above 1.1 and therefore markedly different from the gravity of the gasoline component of the fuel, which ranges around 0.7.
• the greater compatibility of the trialkyl phosphines in this respect promotes the maintenance of good distribution of the additive throughout the gasoline.
• the preferred trialkyl phosphines in which the alkyl groups are in the range from C2 to C4, have boiling points which either lie in or lie close to the boiling range of automotive gasoline.
• the C4 species tri-n-butyl phosphine, has the highest boiling point of the preferred class, around 465 R, which is slightly above the usual gasoline end-point. Nevertheless, in admixture with the gasoline, this substance presents no significant difference from the heavier gasoline fractions in volatility characteristic because of the familiar partial pressure effect. Even the methyl species, boiling separately at little over 100 F. and therefore in the range of the lightest gasoline fractions, creates no incompatibility in volatility characteristic when mixed with the gasoline.
• trialkyl phosphines generally, and Without discrimination among the different species, be used as an additive to diesel fuels for compression ignition engines. See Nygaard et 211., U. S. P. No. 2,368,866. The stated purpose and result were to shorten the ignition delay period of such engines or, in other Words, to accelerate the ignition of the fuel when compressed. To that end, the amount of trialkyl phosphine used was from 0.1% to 5.0%, and preferably from about 0.25% to about 2.0%.
• a fuel for higher compression internal combustion engines employing spark ignition which comprises high octane gasoline as a predominant component together with tetraethyl lead and from .005 to .025 by volume of at least one trialkyl phosphine selected from the class of such phosphines in which the alkyl groups are selected from the group consisting of C1 to C3 alkyl groups,
• a fuel for higher compression internal combustion engines employing spark ignition which comprises high octane gasoline as a predominant component together with tetraethyl lead and from .005% to .025 by volume of at least one trialkyl phosphine selected from the class of such phosphines in which the alkyl groups are selected from the group consisting of C1 to C3 alkyl groups, primary and secondary C4 alkyl groups and primary C5 alkyl groups, with the proviso that at least two of the alkyl groups are selected from the group consisting of C2 to C3 alkyl groups and primary and secondary C4 alkyl groups.
• a fuel for higher compression internal combustion engines employing spark ignition which comprises high octane gasoline as a predominant component together with tetraethyl lead and from about 0.2 cc./gal. to about 0.5 cc./gal. of at least one trialkyl phosphine selected from the class of such phosphines in which the alkyl groups are selected from the group consisting of C1 to C3 alkyl groups, primary and secondary C4 alkyl groups and primary C5 alkyl groups.
• a fuel for higher compression internal combustion engines employing spark ignition which comprises high octane gasoline as a predominant component together with tetraethyl lead and from about 0.2 cc./gal. to about 0.5 cc./gal. of at least one trialkyl phosphine selected from the class of such phosphines in which the alkyl groups are selected from the group consisting of C1 to C alkyl groups, primary and secondary C4 alkyl groups and primary C5 alkyl groups, with the proviso that at least two of the alkyl groups are selected from the group consisting of C2 and C3 alkyl groups and primary and secondary C4 alkyl groups.
• a fuel for higher compression internal combustion engines employing spark ignition which comprises high octane gasoline as a predominant component together with about 3 cc./gal. of tetraethyl lead and about 0.3 cc./ gal. of triethyl phosphine.
• a fuel for higher compression internal combustion engines employing spark ignition which comprises high octane gasoline as a predominant component together with about 3 cc./ga1. of tetraethyl lead and about 0.4 cc./gal. of tripropyl phosphine.
• a fuel for higher compression internal combustion engines employing spark ignition which comprises high octane gasoline as a predominant component together With about 3 cc./gal. of tetraethyl lead and about 0.5 cc./gal. of tributyl phosphine.

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• Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Liquid Carbonaceous Fuels (AREA)
• Solid Fuels And Fuel-Associated Substances (AREA)

Priority Applications (8)

Applications Claiming Priority (1)

Publications (1)

Family

ID=24038627

Family Applications (1)

Country Status (7)

Cited By (17)

Citations (6)

• 0
  • NL NL102666D patent/NL102666C/xx active
  • BE BE548250D patent/BE548250A/xx unknown
  • NL NL207558D patent/NL207558A/xx unknown
• 1955
  • 1955-05-31 US US512325A patent/US2797153A/en not_active Expired - Lifetime
• 1956
  • 1956-05-29 DE DES48879A patent/DE1051566B/de active Pending
  • 1956-05-30 CH CH352184D patent/CH352184A/de unknown
  • 1956-05-30 GB GB16718/56A patent/GB840088A/en not_active Expired
  • 1956-05-30 ES ES0228864A patent/ES228864A1/es not_active Expired

Patent Citations (6)

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