US3082070A - Motor fuel containing synergistic octane appreciator - Google Patents

Motor fuel containing synergistic octane appreciator Download PDF

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US3082070A
US3082070A US789529A US78952959A US3082070A US 3082070 A US3082070 A US 3082070A US 789529 A US789529 A US 789529A US 78952959 A US78952959 A US 78952959A US 3082070 A US3082070 A US 3082070A
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octane
alcohol
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carbon atoms
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George W Eckert
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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
    • 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
    • C10L1/18Organic 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
    • C10L1/188Carboxylic acids; metal salts thereof
    • 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
    • C10L1/19Esters ester radical containing compounds; ester ethers; carbonic acid esters
    • 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
    • C10L1/20Organic compounds containing halogen
    • C10L1/201Organic compounds containing halogen aliphatic 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
    • 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)
    • C10L1/306Organic compounds compounds not mentioned before (complexes) organo-metallic compounds (containing a metal to carbon bond) organo Pb compounds

Definitions

  • Catalytic cracking and catalytic reforming which are the most Widely used refining operations in the production or high octane fuels, produce substantial quantities of aromatics; catalytic cracking also produces a substantial amount of olefins.
  • olefins and aromatics although possessing high octane ratings have a poorer response to organo-lead compounds such as tetraethyl lead than saturated aliphatic gasoline components. Accordingly, as the aromatic and olefinic content of the gasolines have increased to meet the octane levels re quired by modern automotive high compression engines, the lead response of the resulting fuels has diminished. Stated another way, the octane increment obtainable by the addition of an organo-lead compound decreases as the aromatic and olefin contents of the base fuel increase.
  • hydrocarbyl monocarboxylic acids substantially raise the octane rating of a motor fuel containing an organo-lead anti-knock agent and a substantial concentration of high octane components which may be aromatic hydrocarbons, olefinic hydrocarbons or mixtures thereof.
  • octane components which may be aromatic hydrocarbons, olefinic hydrocarbons or mixtures thereof.
  • t-alkyl esters of hydrocarbyl monocarboxylic acids have a similar octane appreciating action on leaded fuels of this composition.
  • Low molecular weight aliphatic alcohols have long been used as components of gasoline fuels, methyl, ethyl, isopropyl and butyl alcohols are known to possess high octane ratings and their use per se and as components of high octane gasoline has been suggested in many patents and publications.
  • the recommended concentration of aliphatic alcohol for improving the octane rating of gasoline blends ranges from about 5 to about 50 or more volume percent of the total fuel.
  • the use of small concentrations of low molecular weight aliphatic alcohols, that is, of the order of 0.2 to 2.0 volume percent has been widely practiced in recent years to impart anti-icing, antistalling properties to gasoline.
  • the subject invention involves the discovery that the octane rating of leaded motor fuels containing a substantial concentration of high octane aromatic and/or olefinic components is markedly improved by the addition of a small amount of a mixture of a hydrocarbyl monocarboxylic acid or a tertiary alkyl ester thereof and an aliphatic alcohol.
  • the high octane hydrocarbon motor fuels of this invention comprise high octane components including a substantial concentration of aromatic hydrocarbons, olefinic hydrocarbons or mixtures thereof, an organo-lead antiknock agent, a hydrocarbyl monocarboxylic acid or a tertiary alkyl ester thereof in a concentration of at least 0.1 volume percent and a low molecular weight aliphatic alcohol in a concentration of at least 0.2 volume percent of the fuel.
  • This invention also is directed to a synergistic octane appreciating mixture comprising 1-50 parts of hydrocarbyl monocarboxylic acid, a tertiary alkyl ester or mixture thereof and 2-100 parts of aliphatic alcohol for use in leaded fuels containing the prescribed aromatic and/or olefin content.
  • This synergistic octane appreciating additive advantageously comprises 2-15 parts of monocarboxylic acid or t-alkyl ester and 5-20 parts low molecular weight aliphatic alcohol.
  • monocarboxylic acids and talkyl esters appear to have little effect on the octane rating of a gasoline consisting essentially of saturated aliphatic hydrocarbons even though an organo-lead anti-knock agent is present.
  • the synergistic octane appreciators comprising a monocarboxylic acid or a tertiary alkyl ester and an aliphatic alcohol is characterized by the same properties and accordingly is effective in a base fuel containing an organo-lead anti-knock agent and a substantial concentration of aromatics and/or olefins.
  • novel fuel compositions of this invention have a minimum concentration of aromatic and/ or olefin components of about 10 volume percent.
  • the aromatic and/or olefin components of the motor fuel of the invention can constitute as high as 100 volume percent thereof but usually fall between 20 and volume percent.
  • a minimum 10 percent concentration appears tobe necessary for the synergistic action of a monocarboxylic acid or its t-alkyl ester and an aliphatic alcohol in improving the octane rating.
  • the aromatic components of the motor fuel of the invention are generally supplied by catalytic reforming or catalytic cracking operations. Catalytic reformate is particularly high in aromatics.
  • the olefin components of the motor fuel of the invent-ion are derived either from thermal cracking, catalytic cracking or polymerization.
  • the organo-lead reagent necessary for the action of the synergistic octane improver is a tctraalkyl lead compound of the class known to possess anti-knock action.
  • Tetraethyl lead is practically universally used as an anti-knock agent but other .tetraalkyl lead compounds such as tetramethyl lead, tetrabutyl lead, tetraamyl lead, tetrapropyl lead, etc. are known to possess anti-knock properties and may be used in the fuel compositions of the invention.
  • Tetraethyl lead mixtures commercially available for automotive use contain an ethylene chloride-ethylene bromide mixture as a scavenger for removing lead from the combustion chamber in the form of volatile lead halides.
  • Tetraethyl lead fluid denotes the commercial product which comprises tetraethyl lead, ethylene chloride and ethylene bromide, the latter two reagents being present in 1.0 theory and 0.5 theory, respectively, theory denoting the stoichiometric amount required for reaction with the lead content of the tetraethyl lead.
  • the organo-lead reagent is present in the fuel compositions of the invention in concentrations between 0.5 ml. per gallon up to the statutory limit of organo lead reagent concentration which, at the present time, is 3 ml. per gallon in the case of automotive fuel and 4.6 ml. per gallon in the case of aviation fuel.
  • the usual concentration of tetraethyl lead is between 1 and 3 ml. per gallon in automotive gasoline and 2-4.6 ml. per gallon in aviation gasoline.
  • the monocarboxylic acid or ester component of the synergistic additive of this invention has the general formula: RCOOR' wherein R is hydrogen or a hydrocarbyl radical containing 129 carbon atoms and R is H or a tertiary alkyl group containing 4-18 carbon atoms.
  • R is advantageously an aliphatic, cycloaliphatic, or aryl radical containing 1-8 :arbon atoms; if R is a t-alkyl group it advantageously :ontains 4-12 carbon atoms.
  • Hydrocarbyl monocarboxylic acids which form synergistic octane appreciators with aliphatic alcohols are the following: acetic acid, formic acid, propionic acid, 2- :thylhexanoic acid, lauric acid, stearic acid, 2-ethylbutyric acid, cumic acid, benzoic acid, cyclohexane carboxylic acid, oleic acid and mixtures thereof.
  • Particularly preferred acids for use in the synergistic octane appreciator at this invention are acetic acid, Z-ethylhexanoic acid, propionic acid, benzoic acid, cyclohexane carboxylic acid and hexanoic acid.
  • Tertiary alkyl esters effective as synergistic octane ap- Jreciators with aliphatic alcohols in the fuel compositions 3f the invention are the following: t-butyl acetate, tabutyl formate, t-amyl propionate, t-arnyl caproate, t-amyl heptanoate, t-octyl pelargonate, t-octyl caprate, t-hutyl lautate, t-buytl myristate, t-amyl palmitate, t-nonyl stearate, ;-amyl behenate, t-dodecyl :butyrate, t-amyl hexanoate, :-dodecyl o-cumate, t-dodecyl benzoate, t-amyl cyclo- 1exane car-boxylate,
  • the preferred tertiary alkyl esters used in the fuel :ompositions of the invention are derived from aliphatic and aromatic monocarboxylic acids containing 1-9 carbon atoms and from a tertiary alkyl radical containing 4-12 :arbon atoms.
  • Preferred tertiary alkyl esters are t-butyl Z-ethylhexanoate, t-butyl benzoate, t-amyl acetate, t-amyl propionate, t-octyl benzoate, t-butyl hexanoate, t-dodecyl sexanoate, tabutyl acetate and t-butyl propionate.
  • the monocarboxylic acid or t-alkyl ester must be present in the leaded aromatic and/or olefin-containing :ompositions of the invention in a minimum concentration at 0.1 volume percent before a synergistic octane appreziation is realized. With acid or ester concentrations below 0.1 volume percent, neither octane improvement per se nor synergistic action with alcohols is obtained in leaded gasoline of prescribed composition.
  • the preferred :oncentration of acid or ester in the synergistic additive falls between 0.2 and 1.5 volume percent with maximum results generally being obtained at a concentration level If about 0.75 volume percent.
  • the aliphatic alcohol component of the synergistic anti- :nock additive of this invention has the general formula: H wherein R is an aliphatic hydrocarby'l radical conaining l-10 carbon atoms.
  • R is an aliphatic hydrocarby'l radical conaining l-10 carbon atoms.
  • the preferred alcohols for 4 use in the synergistic anti-knock additive of the invention contain l-6 carbon atoms since the lower alcohols not only display a maximum synergistic octane appreciating action with the t-alkyl esters but they are effective antiicing agents.
  • alcohols which react synergistically with t-alkyl esters are methyl alcohol, ethyl alcohol, isopropyl alcohol, n-propyl alcohol, isobutyl alcohol, secondary butyl alcohol, tabutyl alcohol, isoamyl alcohol, n-hexyl alcohol, 2-ethylhexanol, isooctyl alcohol and t-am-yl alcohol.
  • Table I there is shown a synergistic octane appreciating action of mixtures of tertiary alkyl esters and methyl alcohol in a gasoline having a Research Octane Number (RON) of 105.
  • the base fuel contained 3 cc. of tetraethyl lead (TEL) per gallon and comprised approximately 10 percent n-butane, 40 percent isobutane-isobutylene alkylate, 10 percent pentenes from fluid catalytically cracked naphtha and 40 percent heavy platformate.
  • TEL tetraethyl lead
  • FIA Fluorescent Indicator Analysis
  • the base fuel had an aromatic content of approximately 35 percent and an olefin content of approximately 6 percent; its 'IBP was and its end point was 367 F.
  • the 105 octane base fuel employed in obtaining the data shown in Table II had the same composition as the base fuel employed.- in Table I.
  • Base Fuel A was a premium grade gasoline containing 3 cc. of TEL per gallon and comprising approximately 50% saturates, 41% aromatics and 9% olefiris by FIA method; base fuel A which had in IBP of 89 F. and an end point of 372 F. had a leaded RON of 100.7.
  • Base fuel B was a regular grade gasoline containing 3 cc. of TEL per gallon and comprising approximately 56% saturates, 22% olefins and 22% aromatics by PIA method; base fuel B which had an IBP of 92 F. and an end point of 367 F., had a leaded RON of about 93.0.
  • This invention is an important advance in the technology of high octane fuels since it provides means whereby the significant octane appreciating action of t-alkyl esters and hydrocarbyl monocanboxylic acids on leaded fuels of prescribed compositions is significantly enhanced using readily available reasonably priced materials which are already widely used as gasoline components for their anti-icing function. It is noteworthy that the fuels of this invention containing a synergistic octane appreciating mixture of a hydrocarbyl monocarboxylic acid or a talkyl ester thereof with a low molecular weight aliphatic alcohol are characterized by the excellent anti-stalling and anti-icing properties as a result of the presence there in of low molecular weight alcohols.
  • a hydrocarbon fuel in the gasoline boiling range containing an alkyl lead anti-knock agent, high octane components selected from the group consisting of olefinic hydrocarbons, aromatic hydrocarbons and mixtures thereof in a concentration of at least 10 volume percent 01 said fuel and a synergistic additive combination of (1) an acidic compound selected from the group consisting of hydrocarbyl monocarboxylic acids containing 1 to 30 carbon atoms, their tertiary alkyl esters and mixtures thereof and (2) a low molecular weight aliphatic alcohol of the general formula: ROl-I wherein R is an aliphatic hydrocarbyl radical containing 1-10 carbon atoms, said acidic compound being present in a concentration between 0.1 and 5.0 volume percent of said fuel and said alcohol being present in a concentration between 0.2 and 5.0 volume percent of said fuel said combination effecting a substantial improvement of the octane rating of said iorgano-lead-containing hydrocarbon fuel.
  • a hydrocarbon fuel in the gasoline boiling range containing an alkyl lead anti-knock agent in a concentration of at least 0.5 cc. per gallon, high octane components selected from the group consisting of olcfinic hydrocarbons, aromatic hydrocarbons, and mixtures thereof, in a concentration of at least 10 volume percent of said fuel, a synergistic additive combination of (1) an acidic compound having the general formula: RCOOR' wherein R is a hydrocarbyl radical containing 1-8 carbon atoms and R is selected from the group consisting of hydrogen and a t-a-lkyl group containing 4-12 carbon atoms, and (2) a low molecular weight aliphatic alcohol having the general formula: ROI-I wherein R is an aliphatic hydrocarbyl radical containing 1-6 carbon atoms, said acidic compound being present in a concentration between 0.1 and 5 .0 volume percent and said alcohol being present in a concentration between 0.2 and 5.0 volume percent.
  • RCOOR' wherein R is
  • a hydrocarbon fuel according to claim 4 in which said acidic compound is present in a concentration of 0.2 to 1.5 volume percent and said alcohol is present in a concentration of 0.5 to 2.0 volume percent.
  • a hydrocarbon fuel according to claim 4 in which said additive combination comprises propionic acid and isopropyl alcohol.
  • a synergistic additive combination according to claim 16 comprising 2 to 15 parts by volume of said acidic compound and 5 to 20 parts by volume of said alcohol.

Description

United States atent 3,082,070 Patented Mar. 19, 1963 3,082,070 MOTOR FUEL CONTAINING SYNERGISTIC OCTANE APPRECIATOR George W. Eckert, Wappingers Falls, N.Y., assignor to Texaco Inc., a corporation of Delaware N Drawing. Filed Jan. 28, 1959, Ser. No. 789,529 18 Claims. (Cl. 4453) This invention relates to a hydrocarbon fuel composition of high octane rating. More specifically, it involves the discovery that the octane rating of leaded gasoline fuels is substantially improved by the addition of synergistic additive mixtures of hydrocarbyl monocarboxylic acids or tertiary alkyl esters thereof with low molecular weight aliphatic alcohols.
The recent increases in compression ratios of automobile engines have placed a severe strain on petroleum refiners to produce fuels having the octane rating demanded by these engines. Premium fuels at the present time have research octane ratings between 97 and 100 and it has been predicted that premium fuels will require octane ratings between 105 and 110 five years from now in order to satisfy the octane requirements of the high compression automotive engines predicted for that date. In order to produce premium fuels of octane ratings of 97 and above, it has been necessary for refiners to rely heavily on catalytic refining operations such as fluid catalytic cracking, catalytic reforming, alkylation and catalytic isomerization.
Catalytic cracking and catalytic reforming, which are the most Widely used refining operations in the production or high octane fuels, produce substantial quantities of aromatics; catalytic cracking also produces a substantial amount of olefins. It is well known that olefins and aromatics, although possessing high octane ratings have a poorer response to organo-lead compounds such as tetraethyl lead than saturated aliphatic gasoline components. Accordingly, as the aromatic and olefinic content of the gasolines have increased to meet the octane levels re quired by modern automotive high compression engines, the lead response of the resulting fuels has diminished. Stated another way, the octane increment obtainable by the addition of an organo-lead compound decreases as the aromatic and olefin contents of the base fuel increase.
In my commonly assigned copending application Serial No. 689,466, filed October 11, 1957, it is disclosed that hydrocarbyl monocarboxylic acids substantially raise the octane rating of a motor fuel containing an organo-lead anti-knock agent and a substantial concentration of high octane components which may be aromatic hydrocarbons, olefinic hydrocarbons or mixtures thereof. In another commonly-assigned copending application Serial No. 699,944, filed December 2, 1957 in the names of George W. Eckert, Howard V. Hess and Edwin C. Knowles, it is disclosed that t-alkyl esters of hydrocarbyl monocarboxylic acids have a similar octane appreciating action on leaded fuels of this composition.
Low molecular weight aliphatic alcohols have long been used as components of gasoline fuels, methyl, ethyl, isopropyl and butyl alcohols are known to possess high octane ratings and their use per se and as components of high octane gasoline has been suggested in many patents and publications. The recommended concentration of aliphatic alcohol for improving the octane rating of gasoline blends ranges from about 5 to about 50 or more volume percent of the total fuel. The use of small concentrations of low molecular weight aliphatic alcohols, that is, of the order of 0.2 to 2.0 volume percent has been widely practiced in recent years to impart anti-icing, antistalling properties to gasoline.
The subject invention involves the discovery that the octane rating of leaded motor fuels containing a substantial concentration of high octane aromatic and/or olefinic components is markedly improved by the addition of a small amount of a mixture of a hydrocarbyl monocarboxylic acid or a tertiary alkyl ester thereof and an aliphatic alcohol.
The high octane hydrocarbon motor fuels of this invention comprise high octane components including a substantial concentration of aromatic hydrocarbons, olefinic hydrocarbons or mixtures thereof, an organo-lead antiknock agent, a hydrocarbyl monocarboxylic acid or a tertiary alkyl ester thereof in a concentration of at least 0.1 volume percent and a low molecular weight aliphatic alcohol in a concentration of at least 0.2 volume percent of the fuel.
This invention also is directed to a synergistic octane appreciating mixture comprising 1-50 parts of hydrocarbyl monocarboxylic acid, a tertiary alkyl ester or mixture thereof and 2-100 parts of aliphatic alcohol for use in leaded fuels containing the prescribed aromatic and/or olefin content. This synergistic octane appreciating additive advantageously comprises 2-15 parts of monocarboxylic acid or t-alkyl ester and 5-20 parts low molecular weight aliphatic alcohol.
The afore-identified copending applications disclose that the action of monocarboxylic acid-s and t-alkyl esters in raising the octane rating of gasoline is. characterized by several unusual features. First, these agents appear to be ineffective in raising the octane rating of gasolines unless an organo-lead anti-knock agent, normally tertaethyl lead, is a component of the gasoline mixture. Second equal concentrations of these agents cause a greater octane improvement above the 100 octane level than below the 100 octane level. Third, monocarboxylic acids and talkyl esters appear to have little effect on the octane rating of a gasoline consisting essentially of saturated aliphatic hydrocarbons even though an organo-lead anti-knock agent is present. The synergistic octane appreciators comprising a monocarboxylic acid or a tertiary alkyl ester and an aliphatic alcohol is characterized by the same properties and accordingly is effective in a base fuel containing an organo-lead anti-knock agent and a substantial concentration of aromatics and/or olefins.
The novel fuel compositions of this invention have a minimum concentration of aromatic and/ or olefin components of about 10 volume percent. The aromatic and/or olefin components of the motor fuel of the invention can constitute as high as 100 volume percent thereof but usually fall between 20 and volume percent. A minimum 10 percent concentration appears tobe necessary for the synergistic action of a monocarboxylic acid or its t-alkyl ester and an aliphatic alcohol in improving the octane rating.
The aromatic components of the motor fuel of the invention are generally supplied by catalytic reforming or catalytic cracking operations. Catalytic reformate is particularly high in aromatics. The olefin components of the motor fuel of the invent-ion are derived either from thermal cracking, catalytic cracking or polymerization.
The organo-lead reagent necessary for the action of the synergistic octane improver is a tctraalkyl lead compound of the class known to possess anti-knock action. Tetraethyl lead is practically universally used as an anti-knock agent but other .tetraalkyl lead compounds such as tetramethyl lead, tetrabutyl lead, tetraamyl lead, tetrapropyl lead, etc. are known to possess anti-knock properties and may be used in the fuel compositions of the invention.
The tetraethyl lead mixtures commercially available for automotive use contain an ethylene chloride-ethylene bromide mixture as a scavenger for removing lead from the combustion chamber in the form of volatile lead halides. Tetraethyl lead fluid denotes the commercial product which comprises tetraethyl lead, ethylene chloride and ethylene bromide, the latter two reagents being present in 1.0 theory and 0.5 theory, respectively, theory denoting the stoichiometric amount required for reaction with the lead content of the tetraethyl lead.
The organo-lead reagent is present in the fuel compositions of the invention in concentrations between 0.5 ml. per gallon up to the statutory limit of organo lead reagent concentration which, at the present time, is 3 ml. per gallon in the case of automotive fuel and 4.6 ml. per gallon in the case of aviation fuel. The usual concentration of tetraethyl lead is between 1 and 3 ml. per gallon in automotive gasoline and 2-4.6 ml. per gallon in aviation gasoline.
The monocarboxylic acid or ester component of the synergistic additive of this invention has the general formula: RCOOR' wherein R is hydrogen or a hydrocarbyl radical containing 129 carbon atoms and R is H or a tertiary alkyl group containing 4-18 carbon atoms. in the above general formula, R is advantageously an aliphatic, cycloaliphatic, or aryl radical containing 1-8 :arbon atoms; if R is a t-alkyl group it advantageously :ontains 4-12 carbon atoms.
Hydrocarbyl monocarboxylic acids which form synergistic octane appreciators with aliphatic alcohols are the following: acetic acid, formic acid, propionic acid, 2- :thylhexanoic acid, lauric acid, stearic acid, 2-ethylbutyric acid, cumic acid, benzoic acid, cyclohexane carboxylic acid, oleic acid and mixtures thereof. Particularly preferred acids for use in the synergistic octane appreciator at this invention are acetic acid, Z-ethylhexanoic acid, propionic acid, benzoic acid, cyclohexane carboxylic acid and hexanoic acid.
Tertiary alkyl esters effective as synergistic octane ap- Jreciators with aliphatic alcohols in the fuel compositions 3f the invention are the following: t-butyl acetate, tabutyl formate, t-amyl propionate, t-arnyl caproate, t-amyl heptanoate, t-octyl pelargonate, t-octyl caprate, t-hutyl lautate, t-buytl myristate, t-amyl palmitate, t-nonyl stearate, ;-amyl behenate, t-dodecyl :butyrate, t-amyl hexanoate, :-dodecyl o-cumate, t-dodecyl benzoate, t-amyl cyclo- 1exane car-boxylate, t-octyl cinnarnate, t-amyl phenyl ace- Late, t-butyl oleate, t-butyl ester of Snodotte acids (byirogenated fish oil acids comprising mainly C to C acids) and t-butyl esters of coconut fatty acids (comprislng mainly a mixture of C to C fatty acids).
The preferred tertiary alkyl esters used in the fuel :ompositions of the invention are derived from aliphatic and aromatic monocarboxylic acids containing 1-9 carbon atoms and from a tertiary alkyl radical containing 4-12 :arbon atoms. Preferred tertiary alkyl esters are t-butyl Z-ethylhexanoate, t-butyl benzoate, t-amyl acetate, t-amyl propionate, t-octyl benzoate, t-butyl hexanoate, t-dodecyl sexanoate, tabutyl acetate and t-butyl propionate.
The monocarboxylic acid or t-alkyl ester must be present in the leaded aromatic and/or olefin-containing :ompositions of the invention in a minimum concentration at 0.1 volume percent before a synergistic octane appreziation is realized. With acid or ester concentrations below 0.1 volume percent, neither octane improvement per se nor synergistic action with alcohols is obtained in leaded gasoline of prescribed composition. The preferred :oncentration of acid or ester in the synergistic additive falls between 0.2 and 1.5 volume percent with maximum results generally being obtained at a concentration level If about 0.75 volume percent. Although acid or ester :oncentrations as high as 5 volume percent can be in- :orporated in the fuel compositions, economic considera- :ions preclude the use of such high concentrations. In addition, it appears there is a fall-otf in octane improvenent after acid or ester concentration exceeds about 1.5 lolume percent.
The aliphatic alcohol component of the synergistic anti- :nock additive of this invention has the general formula: H wherein R is an aliphatic hydrocarby'l radical conaining l-10 carbon atoms. The preferred alcohols for 4 use in the synergistic anti-knock additive of the invention contain l-6 carbon atoms since the lower alcohols not only display a maximum synergistic octane appreciating action with the t-alkyl esters but they are effective antiicing agents. Examples of alcohols which react synergistically with t-alkyl esters are methyl alcohol, ethyl alcohol, isopropyl alcohol, n-propyl alcohol, isobutyl alcohol, secondary butyl alcohol, tabutyl alcohol, isoamyl alcohol, n-hexyl alcohol, 2-ethylhexanol, isooctyl alcohol and t-am-yl alcohol.
Although minimum concentration of alcohol for synergistic octane improvement is set at 0.2 volume percent, the preferred alcohol concentration employed in the synergistic anti-knock additive of the invention falls between about 0.5 and 2.0 volume percent. Although it has been found that concentrations as high as 10 volume percent alcohol can be used in synergistic combination with acids or t-alkyl esters, alcohol concentrations above about 3.0 volume percent are uneconomic.
In Table I there is shown a synergistic octane appreciating action of mixtures of tertiary alkyl esters and methyl alcohol in a gasoline having a Research Octane Number (RON) of 105. The base fuel contained 3 cc. of tetraethyl lead (TEL) per gallon and comprised approximately 10 percent n-butane, 40 percent isobutane-isobutylene alkylate, 10 percent pentenes from fluid catalytically cracked naphtha and 40 percent heavy platformate. By Fluorescent Indicator Analysis (FIA) the base fuel had an aromatic content of approximately 35 percent and an olefin content of approximately 6 percent; its 'IBP was and its end point was 367 F.
TABLE I Units Improvement in RON With Mixtures of Tertiary Alkyl Esters and Methyl Alcohols in Octane Gasoline Concentration of methyl alcohol, volume percent Ester concentration The data in Table I show clearly the synergistic octane appreciating action of mixtures of methyl alcohol and t-alkyl esters in leaded high octane gasoline having the prescribed aromatic and/or olefin content. It will be noted that methyl alcohol in amounts up to about 2.0 volume percent, has substantially no octane appreciating action. As the concentration of methyl alcohol increases from 3 to about 7.5 volume percent the octane appreciating action of the alcohol alone rises from about 1 RON unit to 3 RON units. It is significant that a synergistic octane appreciating action is obtained with mixtures of t-alkyl esters and methyl alcohol throughout the whole range of alcohol concentration.
The synergistic action of the t-alkyl esters with methyl alcohol is exemplified in Table I by the fact that a mixture of 0.75 percent t-butyl acetate and 1.0 percent methyl alcohol appreciates the octane rating of 105 octane gasoline by 2.5 units whereas only a 1.9 unit improvement would be expected if the additives acted independently. Similarly, a mixture of 0.75 percent t-butyl acetate and 2.0 percent methyl alcohol effected a 3.2 unit improvement whereas only a 2.0 unit octane improvement would have been obtained if the additives acted independently.
In Table II there is shown the octane appreciating action of t-alkyl esters with C to C aliphatic alcohols.
The 105 octane base fuel employed in obtaining the data shown in Table II had the same composition as the base fuel employed.- in Table I.
TABLE II Units Improvement in RON With Mixtures of t-Butyl Esters and Aliphatic Alcohols Additive: Increase in RON 0.75% t-butyl acetate 1.8 0.75% t-butyl propionate 1.7 1.0% ethyl alcohol 0.0 1.0% isopropyl alcohol 0.0 1.0% t-butyl alcohol 0.0 1.0% sec-butyl alcohol 0.0 1.0% isobutyl alcohol 0.0 1.0% n-butyl alcohol 0.0 2.0% Z-ethylbutanol 0.0
0.75% t-buty1acetate+l.0% ethyl alcohol 2.9 0.75% t-butyl acetate+l.0% isopropyl alcohoL 3.0 [0.75% t-butyl acetate-{4.0% sec-butyl alcohol- 2.5 0.75% t-butyl acetate+1.0% isobutyl alcohol 2.8 0.75% t-butyl acetate+l.0% n-butyl alcohol"- 2.7 0.75% tbutyl acetate+2.0% 2-ethylbutanol 2.6 0.75% t-butyl propionate+1.0% isopropyl alco- 5 hol 2. 0.75% t-buty1acetate+l.0% t-butyl alcohoL" 2.
The synergistic action of t-alkyl esters and methyl alcohol in regular and premium gasolines is shown in Table III. Base Fuel A was a premium grade gasoline containing 3 cc. of TEL per gallon and comprising approximately 50% saturates, 41% aromatics and 9% olefiris by FIA method; base fuel A which had in IBP of 89 F. and an end point of 372 F. had a leaded RON of 100.7.
Base fuel B Was a regular grade gasoline containing 3 cc. of TEL per gallon and comprising approximately 56% saturates, 22% olefins and 22% aromatics by PIA method; base fuel B which had an IBP of 92 F. and an end point of 367 F., had a leaded RON of about 93.0.
TABLE III Units Improvement in RON With Mixtures of t-Butyl Acetate and Methyl Alcohol Increase in RON The data in Table 111 show clearly the synergistic octane appreciating action of mixtures of t-butyl acetate and methyl alcohol in regular and premium .grade gasoline. "It is significant that a greater increase in RON is obtained with the synergistic mixture in the premium fuel than in the regular fuel. Comparison with the results shown in Tables I and II indicate that an even greater increase in RON is obtained with the synergistic mixture when the octane level reaches 105. This property of the synergistic mixture is akin to the action of monocarboxylic acids and its t-alkyl esters as disclosed in the af-ore-identified copending applications Serial Nos. 689,466 and 699,944.
In Table IV there is shown the synergistic octane appreciating action of mixtures of hydrocarbyl monocarboxylic acids and alcohols in the 105 octane base fuel employed in Table I.
y 6 TABLE IV Units Improvement in RON With Mixtures of Monoca-rboxylic Acids and Aliphatic Alcohols in Octane Gasoline Additive: Increase in RO-N 1.0% methyl alcohol 0.1 1.0% isopropyl alcohol 0.( 1.0% t-butyl alcohol 0C 0.5% 2-ethylhexanoic acid 2.7 0.3% propionic acid 2.6 0.5% benzoic acid 3.4 0.5 Z-ethylhexanoic acid+1.0% methyl alcohol 3.5 0.3% propionic acid|1.0% methyl alcohol 3.] 0.3% propionic acid|1.0% isopropyl alcohoLo 4.2 0.5 benzoic acid+1.0% t-butyl alcohol 3.8
The data in Table IV demonstrate the synergistic octane appreciating action of mixtures of hydrocarbyl monocarboxylic acids and aliphatic alcohols in a leaded gasoline containing the prescribed aromatic and/ or olefin content.
This invention is an important advance in the technology of high octane fuels since it provides means whereby the significant octane appreciating action of t-alkyl esters and hydrocarbyl monocanboxylic acids on leaded fuels of prescribed compositions is significantly enhanced using readily available reasonably priced materials which are already widely used as gasoline components for their anti-icing function. It is noteworthy that the fuels of this invention containing a synergistic octane appreciating mixture of a hydrocarbyl monocarboxylic acid or a talkyl ester thereof with a low molecular weight aliphatic alcohol are characterized by the excellent anti-stalling and anti-icing properties as a result of the presence there in of low molecular weight alcohols.
The selectivity of the synergistic octane appreciating action of mixtures of 'taalkyl esters 'with alcohols was demonstrated by the fact that mixtures comprising 0.75 percent t-bu tyl acetate and various other oxygenated hydnocarbon derivatives gave the same or poorer octane appreciation than that obtained with 0.75 percent t-butyl acetate alone. Table III lists the oxygenated hydrocarbon-s which display no synergistic octane appreciating action with t-butyl acetate.
Obviously, many modifications and variations of the invention as hereinbefore set forth may be made without departing from the spirit and scope thereof and, therefore, only such limitations should be imposed as are indicated in the appended claims.
I claim:
1. A hydrocarbon fuel in the gasoline boiling range containing an alkyl lead anti-knock agent, high octane components selected from the group consisting of olefinic hydrocarbons, aromatic hydrocarbons and mixtures thereof in a concentration of at least 10 volume percent 01 said fuel and a synergistic additive combination of (1) an acidic compound selected from the group consisting of hydrocarbyl monocarboxylic acids containing 1 to 30 carbon atoms, their tertiary alkyl esters and mixtures thereof and (2) a low molecular weight aliphatic alcohol of the general formula: ROl-I wherein R is an aliphatic hydrocarbyl radical containing 1-10 carbon atoms, said acidic compound being present in a concentration between 0.1 and 5.0 volume percent of said fuel and said alcohol being present in a concentration between 0.2 and 5.0 volume percent of said fuel said combination effecting a substantial improvement of the octane rating of said iorgano-lead-containing hydrocarbon fuel.
2. A hydrocarbon fuel according to claim 1 in which said acidic compound has the general formula: RCOOR' wherein R is selected from the group consisting of hydrogen and hydrocarbyl radicals containing 1-29 carbon atoms, and R is selected from the group consisting of hydrogen and a t-al kyl group containing 4-18 carbon atoms.
3. A hydrocarbon fuel according to claim 1 in which said alkyl lead anti-knock agent is present in a concentration between 0.5 and 4.6 cc. per gallon.
4. A hydrocarbon fuel in the gasoline boiling range containing an alkyl lead anti-knock agent in a concentration of at least 0.5 cc. per gallon, high octane components selected from the group consisting of olcfinic hydrocarbons, aromatic hydrocarbons, and mixtures thereof, in a concentration of at least 10 volume percent of said fuel, a synergistic additive combination of (1) an acidic compound having the general formula: RCOOR' wherein R is a hydrocarbyl radical containing 1-8 carbon atoms and R is selected from the group consisting of hydrogen and a t-a-lkyl group containing 4-12 carbon atoms, and (2) a low molecular weight aliphatic alcohol having the general formula: ROI-I wherein R is an aliphatic hydrocarbyl radical containing 1-6 carbon atoms, said acidic compound being present in a concentration between 0.1 and 5 .0 volume percent and said alcohol being present in a concentration between 0.2 and 5.0 volume percent.
5. A hydrocarbon fuel according to claim 4 in which said acidic compound is present in a concentration of 0.2 to 1.5 volume percent and said alcohol is present in a concentration of 0.5 to 2.0 volume percent.
6. A hydrocarbon fuel according to claim 4 in which said additive combination comprises t-butyl acetate and methyl alcohol.
7. A hydrocarbon fuel according to claim 4 in which said additive combination comprises -t-butyl propionate and methyl alcohol.
8. A hydrocarbon fuel according to claim 4 in which said additive combination comprises t-butyl acetate and isopropyl alcohol.
9. A hydrocarbon fuel according to claim 4 in which said additive combination comprises t-butyl acetate and ethyl alcohol.
10. A hydrocarbon fuel according to claim 4 in which said additive combination comprises t-amyl acetate and methyl alcohol.
11. A hydrocarbon fuel according to claim 4 in which said additive combination comprises t-butyl acetate and t-butyl alcohol.
12. A hydrocarbon fuel according to claim 4 in which said additive combination comprises propionic acid and methyl alcohol.
13. A hydrocarbon fuel according to claim 4 in which said additive combination comprises propionic acid and isopropyl alcohol.
14. A hydrocarbon fuel according to claim 4 in which said additive combination comprises 2-ethylhexanoic acid and methyl alcohol.
15. A hydrocarbon fuel according to claim 4 in which said additive combination comprises benzoic acid and t-butyl alcohol.
16. A synergistic octane appreciating additive for leaded fuels containing a substantial concentration of high octane components selected from the group consisting of aromatic and olefinic hydrocarbons and mixtures thereof consisting of 1-50' parts by volume of an acidic compound having the general formula: RCOO-R wherein R is selected from the group consisting of hydrogen and hydrocarbyl radicals containing 1-29 carbon atoms and R is selected from the group consisting of hydrogen and a t-alkyl group containing 4-18 carbon atoms and 2-100 parts by volume of a low molecular weight aliphatic alcohol of the general formula: ROI-I wherein R is an aliphatic hydrocarbyl radical containing 1-10 carbon atoms.
17. A synergistic additive combination according to claim 16 comprising 2 to 15 parts by volume of said acidic compound and 5 to 20 parts by volume of said alcohol.
18. A synergistic octan'e appreciating additive according to claim 16 in which said acidic compound has the general formula: RCOOR' wherein R is a hydrocarbyl radical containing 1-8 carbon atoms and R is selected from the group consisting of hydrogen and a t-alkyl group containing 4-12 carbon atoms and said alcohol has the general formula: ROI-I wherein R is an aliphatic hydrocarbyl radical containing 1-6 carbon atoms.
References Cited in the file of this patent UNITED STATES PATENTS 1,420,006 Whitaker June 20, 1922 1,423,049 Tunison July 18, 1922 1,423,058 Whitaker July 18, 1922 1,692,784 Orelu-p et al. Nov. 20, 1928 1,752,724 Bourie Apr. 1, 1930 1,757,837 Johns May 6, 1930 2,210,942 Lipkin Aug. 13, 1940 2,218,137 Pyzel Oct. 15, 1940 2,228,662 Holm Jan. 14, 1941 2,403,268 Davis et a1 July 2, 1946 2,409,156 Schulze et a1. Oct. 8, 1946 2,789,891 Brandes et al Apr. 23, 1957 2,884,315 Barnum Apr. 28, 1959 FOREIGN PATENTS 277,326 Great Britain Jan. 7, 1929 640,311 France July 10, 1928 837,965 France Feb. 23, 1939 OTHER REFERENCES Improved Motor Fuels Through Selective Blending, Wagner et al., Paper presented before American Petroleum Institute, Nov. 7, 1941.

Claims (1)

16. A SYNERGISTIC OCTANE APPRECIATING ADDITIVE FOR LEADED FUELS CONTAINING A SUBSTANTIAL CONCENTRATION OF HIGH OCTANE COMPONENTS SELECTED FROM THE GROUP CONSISTING OF AROMATIC AND OLEFINIC HYDROCARBONS AND MIXTURES THEREOF CONSISTING OF 1-50 PARTS BY VOLUME OF AN ACIDIC COMPOUND HAVING THE GENERAL FORMULA: RCOOR'' WHEREIN R IS SELECTED FROM THE GROUP CONSISTING OF HYDROGEN AND HYDROCARBYL RADICALS CONTAINING 1-29 CARBON ATOMS AND R'' IS SELECTED FROM THE GROUP CONSISTING OF HYDROGEN AND A T-ALKYL GROUP CONTAINING 4-18 CARBON ATOMS AND 2-100 PARTS BU VOLUME OF A LOW MOLECULAR WEIGHT ALIPHATIC ALCOHOL OF THE GENERAL FORMULA: ROH WHEREIN R IS ALIPHATIC HYDROCARBYL RADICAL CONTAINING 1-10 CARBON ATOMS.
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FR2050049A5 (en) * 1969-06-06 1971-03-26 Exxon Research Engineering Co
US3903251A (en) * 1971-01-21 1975-09-02 Canadian Ind Gasoline production
US3976437A (en) * 1972-06-23 1976-08-24 Sun Ventures, Inc. Composition comprising a methyl phenol and an ether for gasoline fuels
US4248182A (en) * 1979-09-04 1981-02-03 Ethyl Corporation Anti-wear additives in diesel fuels
FR2520376A1 (en) * 1982-01-22 1983-07-29 Barclay John Rawson ADDITIVE FOR FUELS AND HYDROCARBON LIQUID FUELS
US4859210A (en) * 1987-01-08 1989-08-22 Basf Aktiengesellschaft Motor fuel or lubricant composition containing polybutyl or polyisobutyl derivatives
US5032144A (en) * 1985-04-29 1991-07-16 Union Oil Company Of California Octane enhancers for fuel compositions
WO1992001770A1 (en) * 1990-07-24 1992-02-06 Maria Gabriella Scopelliti Process to prevent water solubilization of alcohols, on their own or in a mixture with hydrocarbons, and additives for such purposes
US6129773A (en) * 1993-07-16 2000-10-10 Killick; Robert William Fuel blends
US20030154649A1 (en) * 2000-01-24 2003-08-21 Angelica Hull Method of reducing the vapor pressure of ethanol-containing motor fuels for spark ignition combustion engines
ES2341519A1 (en) * 2008-10-13 2010-06-21 Fundacion Investigacion E Innovacion Para El Desarrollo Social System to obtain greater energy efficiency through the addition of formic acid to gasoline and gasoline. (Machine-translation by Google Translate, not legally binding)

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FR2050049A5 (en) * 1969-06-06 1971-03-26 Exxon Research Engineering Co
US3903251A (en) * 1971-01-21 1975-09-02 Canadian Ind Gasoline production
US3976437A (en) * 1972-06-23 1976-08-24 Sun Ventures, Inc. Composition comprising a methyl phenol and an ether for gasoline fuels
US4248182A (en) * 1979-09-04 1981-02-03 Ethyl Corporation Anti-wear additives in diesel fuels
FR2520376A1 (en) * 1982-01-22 1983-07-29 Barclay John Rawson ADDITIVE FOR FUELS AND HYDROCARBON LIQUID FUELS
US5032144A (en) * 1985-04-29 1991-07-16 Union Oil Company Of California Octane enhancers for fuel compositions
US4859210A (en) * 1987-01-08 1989-08-22 Basf Aktiengesellschaft Motor fuel or lubricant composition containing polybutyl or polyisobutyl derivatives
WO1992001770A1 (en) * 1990-07-24 1992-02-06 Maria Gabriella Scopelliti Process to prevent water solubilization of alcohols, on their own or in a mixture with hydrocarbons, and additives for such purposes
US6129773A (en) * 1993-07-16 2000-10-10 Killick; Robert William Fuel blends
US20030154649A1 (en) * 2000-01-24 2003-08-21 Angelica Hull Method of reducing the vapor pressure of ethanol-containing motor fuels for spark ignition combustion engines
US20040123516A1 (en) * 2000-01-24 2004-07-01 Angelica Hull Method for making a fuel for a modified spark ignition combustion engine, a fuel for a modified spark ignition combustion engine and a fuel additive for a conventional spark ignition combustion engine
US6761745B2 (en) 2000-01-24 2004-07-13 Angelica Hull Method of reducing the vapor pressure of ethanol-containing motor fuels for spark ignition combustion engines
US7323020B2 (en) 2000-01-24 2008-01-29 Angelica Hull Method for making a fuel for a modified spark ignition combustion engine, a fuel for a modified spark ignition combustion engine and a fuel additive for a conventional spark ignition combustion engine
ES2341519A1 (en) * 2008-10-13 2010-06-21 Fundacion Investigacion E Innovacion Para El Desarrollo Social System to obtain greater energy efficiency through the addition of formic acid to gasoline and gasoline. (Machine-translation by Google Translate, not legally binding)

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