US3031279A - Motor fuel - Google Patents

Motor fuel Download PDF

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US3031279A
US3031279A US793278A US79327859A US3031279A US 3031279 A US3031279 A US 3031279A US 793278 A US793278 A US 793278A US 79327859 A US79327859 A US 79327859A US 3031279 A US3031279 A US 3031279A
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oxidate
fuel
lubricating oil
neut
percent
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US793278A
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Stanley R Newman
Herbert E Vermillion
Bruce S Bailey
Alpert Norman
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Texaco Inc
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Texaco Inc
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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
    • C10L1/16Hydrocarbons
    • C10L1/1616Hydrocarbons fractions, e.g. lubricants, solvents, naphta, bitumen, tars, terpentine
    • 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
    • C10L1/1805Organic compounds containing oxygen oxidised hydrocarbon fractions
    • C10L1/1808Organic compounds containing oxygen oxidised hydrocarbon fractions oxidised mineral waxes
    • 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

  • This invention relates to an improved motor fuel characterized by a plurality of improved properties. More particularly, it involves the discovery that a three-component additive comprising a light distillate lubricating oil, a hydrocarbon oxidate, and a tetraethyl lead mixture containing a prescribed amount of excess ethylene bromide is outstanding as a motor fuel additive for reducing combustion chamber deposits and their side effects, particularly preignition and octane requirement increase.
  • the two-component additive mixture was shown to impart to a motor 'fuel the following advantages: improved road octane, anti-rust and antistalling properties, reduced engine wear, improved valve performance and life, reduced preignition, reduced induction system deposits, better fuel economy, reduced spark plug fouling and improved octane requirement increase.
  • the subject invention involves the discovery that the combination of the light distillate oil-hydrocarbon oil oxidate with a tetraethyl lead mixture containing a prescribed amount of excess ethylene bromide yields a superior motor fuel from the standpoint of reduced engine deposits.
  • the superior motor fuel of this invention contains (1) 0.2 to 1.0 weight percent of a light distillate mineral lubricating oil fraction having an SUS viscosity at 100 F. between 50 and 300, (2) 0.002 to 0.015 weight percent of a hydrocarbon oxidate which is either an ester-type oxidate derived from deoiled macrocrystalline wax having a neutralization (neut.) no. between 60 and 100, a saponification (sap.) no. above 170, a neut. no. to sap. no. ratio between 0.25 and 0.5 and an unsaponifiable content less than 40 percent, or a paraffinic lubricating oil oxidate having a neut. no. between 55 and 80 and a sap. no.
  • tetraethyl lead containing a scavenger mixture consisting of 1.0 theory ethylene chloride and 0.55 to 1.0 theory ethylene bromide, theory denoting the stoichiometric amount required for reaction with the lead content of the tetraethyl lead.
  • the ethylene bromide content of the tetraethyl lead employed in the motor fuel'of this invention is 0.05 to 0.5
  • Tetraethyl lead fluid the commercial product, consists of tetraethyl lead, 1.0 theory ethylene chloride and 0.5 theory ethylene bromide, theory denoting the stoichiometric amount required for reaction with the lead content of the tetraethyl lead.
  • the light lubricating oil component may be a naphthene base distillate, a parafiin base distillate or mixtures thereof, but must have a low carbon residue and an SUS viscosity at F. between 50 and 300.
  • a distillate lubricating oil fraction of this type is obtained by vacuum distillation of a naphthene, paraflin or mixed base lubrieating oil at approximately 20 to 40 mm. pressure and subsequent acid treatment of the distillate.
  • the lubricating oil component generally used has an SUS viscosity at 100 F. of about 100.
  • the light lubricating oil component of the additive mixture should have a Conradson carbon content below 0.02 percent and a viscosity within the prescribed range in order for the gasoline to show best results from the standpoint of engine cleanliness.
  • the lubricating oil component constitutes 0.2 to 1.0 weight percent of the finished gasoline of this invention.
  • the preferred concentration of this component is in the range of 0.3 to 0.8 weight percent, with approximately 0.6 weight percent usually employed.
  • a concentration of 0.6 weight percent is obtained by adding to gasoline about 0.5 percent by volume of a lubricating oil fraction having an SUS viscosity at 100 F. of about 100.
  • the ester-type wax oxidate component obtained by air oxidation of deoiled macrocrystalline wax is the product which is described in detail in the commonly assigned copending application, Serial No. 712,073, now US. 2,894,970, filed January 30, 1958, as a continuation-inpart of Serial No. 427,653, now abandoned filed May 4, 1954, in the names of I. K. McKinley, R. F. Nelson and G. S. Bright.
  • the ester-type oxidate has a neut. no. of 60 to 100, a sap. no. above 170 and a neut. no to sap. no. ratio between 0.25 and 0.5 and preferably between 0.3 and 0.4.
  • the ester type wax oxidate is obtained by air oxidation of a deoiled macrocrystalline wax containing less than 5 percent oil and 20 to 33 carbon atoms per molecule at a temperature between 300 and 350 F., a
  • An ester-type oxidate which has given superior results in the motor fuel of this invention has been prepared from a to 127 F. melting point and semi-refined paraflin wax separated from a distillate oil of about SAE 20 grade and having about 25 to 30 carbon atoms per molecule.
  • the 125 to 127 F. melting point wax which contains about 0.2 to 0.4 percent oil, is separated from the distillate oil by solvent dewaxing with a solvent such as methyl ethyl ketone-toluene mixture.
  • the con' ditions employed in the oxidation of this particularly effective oxidate are a temperature of about 330 F,
  • This ester-type wax oxidate has a neut. no. of about 80, a sap. no. of about 230, a neut. no. to sap. no. ratio of about 0.38 and an unsaponifiable content of about 33 percent.
  • the parafiinic oil oxidate component obtained by catalytic air oxidation of a refined parafiin base lubricating oil is the product described in detail in the commonly assigned copending application Serial No. 710,856, now US. Patent No. 2,978,472, filed January 24, 1958, in the names of George B. Kirkwood and John H. Greene.
  • the parafiinic oil oxidate has a neut. 110. between 55 and 80, a sap. no. between about 100 and 200, an unsaponifiable content less than about 55 percent, a viscosity less than 200 Saybolt Universal seconds (SUS) at 210 F., a color rating less than 200 in the Lovibond /2 cell, and a pour point less than 30 F.
  • the preferred liquid oxidates of this invention have a neut. no. between 60 and 70, a sap. no. between 120 and 165, an unsaponifiable contact less than 55 percent, a viscosity less than 100 SUS at 210 F., a Lovibond /2" cell color rating of less than 100 and a pour point less than about 10 F.
  • the paraffin oil oxidate is obtained by reacting a refined paraflinic lubricating oil having a viscosity of between 90 and'350 SUS at 100 F., preferably between 140 and 180 SUS at 100 F., a pour point less than 10 F., preferably less than 5 F., a Lovibond /2 cell color rating of less than and an aniline point between 210-230 F preferably between 215 and 225 F. with air in the presence of a metalliferous oxidation catalyst in a catalytic amount, e.g., between about 0.1 and 2 percent by weight of the charge oil, at an air feed rate of about 8-50 cu. ft./lb.
  • the preferred conditions are an air feed rate of 1025 cu. ft./lb. oil/hr., an air velocity of about 0.2 to 1 ft./sec., an oxidation initiation temperature of 330-370 F., an oxidation reaction temperature of 260300 F., 50-90 p.s.i.g. and potassium permanganate catalyst in an amount of about 0.4 to 1.2 percent by weight of the charge oil, more preferably in the range of about 1 to 1.2 percent.
  • the oxidation is continued until the oil is oxidized to a neut. no. between about 55 and 80, preferably between 60 and 70. Approximately between 1-6 hours reaction time is necessary to arrive at a neut. no. in the specified range.
  • the liquid oxidate is rapidly cooled to below about 200 F. prior to removal from the reactor at a cooling rate of about 5 to 50 F./ minute, preferably between about 10 to F./minute.
  • the oxidate is then withdrawn from the reactor and filtered to remove any solids contained therein.
  • the oxidate constitutes a very minor portion of the fuel composition of the invention, its concentration falling within the range of 0.002 to 0.015 weight percent of the finished gasoline.
  • the usual concentration of the oxidate material is in the neighborhood of 0.004 to 0.008 weight percent of the finished gasoline. Concentrations of oxidate in excess of 0.015 weight percent degrade the properties of the fuel particularly in the matter of the combustion chamber and intake system deposits. If the concentration is below the prescribed lower limit, the fuel does not show the improved performance characteristics.
  • the oxidate is usually incorporated in the motor fuel in the solution of the distillate mineral oil.
  • the preferred concentration of oxidate is between 0.004 and 0.006 weight percent.
  • a mixture containing a proper proportion of components is prepared by incorporating about 0.057 lb. of oxidate in a gallon of mineral oil having an SUS at 100 F. of about 100.
  • the resulting solution which contains approximately 0.8 percent oxidate is characterized by a neut. no. of about 0.5, a pour. point of -53 R, an SUS viscosity at 100 F. of about 105 and a gravity of 22.4 API.
  • the use of about 0.5 percent by volume of this solution to the motor fuel gives a gasoline containing approximately 0.005 percent oxidate and 0.6 percent lubricating oil.
  • Tetraethyl lead is present in the motor fuels of this invention. in amounts between 1 and 3 ml. per gallon. The upper limit of 3 ml. is set by Federal regulation,
  • the lower limit is generally a function of the refiners need.
  • the usual tetraethyl lead concentration falls between 2 and 3 ml. per gallon of gasoline.
  • the scavenger mixture comprising 1.0 theory ethylene chloride and 0.55 to 1.0 theory ethylene bromide is introduced into the fuel in combination with the tetraethyl lead.
  • the superior performance of the improved motor fuel of this invention has been demonstrated in laboratory bench tests and in high speed and low speed road tests.
  • the laboratory bench tests are the type usually employed to evaluate the properties of the motor fuels and will be described in more detail hereafter.
  • a 20,000 mile road test was run at high speed temperature conditions, specifically at 65 miles per hour in two 8-hour shifts per day in the San Antonio, Texas, area; this test was designed to evaluate the performance of the motor fuel under heavy duty conditions.
  • a 6,000 mile road test was run under low speed, low temperature, stop and go driving conditions, specifically at 35 miles per hour in three 6-hour and 20 minute shifts per day in the Steamboat Springs, Colorado, area; this test was designed to evaluate the performance of the motor fuel under normal driving conditions.
  • Compression rings were weighed to they nearest milligram and gapped to the nearest 0.00025" before and after the test to determine wear. Rings were cleaned with L-4 type cleaning solution and polished with metal polish before measurements were taken.
  • Cylinder bores were measured to the nearest 0.00025" at the center of, the top ring at top and bottom stroke perpendicular and parallel to thecrankshaft on all cylinders before and after test.
  • Air cleaners were disassembled, thoroughly cleaned with solvent and reassembled after oiling the element or filling with new oil (if oil bath-type) of the kind used in the engine crankcase.
  • the reference fuel employed in the road tests was a high quality premium grade fuel comprising mainly fluid catalytically cracked stock and straight run gasoline.
  • the reference fuel had a ASTM research octane rating, contained 2.74 ml. per gallon of tetraethyl lead contaim ing 1.0 theory ethylene chloride and 0.5 theory ethylene bromide, had an API gravity of 60 to 65 and a boiling point range between 100 and 398 F.; the base fuel was negative in the copper corrosion test and had an oxidation stability in the ASTM test of 240 minutes minimum.
  • the reference fuel also contained minor amounts of conventional gasoline inhibitors, for example, approximately 6 pounds of N-N'-disecondary butyl-p-phenylenediamine, a gum inhibitor, per thousand barrels of gasoline, about 1.2 pounds of N-N-disalicylidene-l.Z-diaminopropane, a metal deactivator, per thousand barrels of gasoline, and about 1.1 pounds of lecithin, a tetraethyl lead stabilizer, per thousand barrels of gasoline.
  • conventional gasoline inhibitors for example, approximately 6 pounds of N-N'-disecondary butyl-p-phenylenediamine, a gum inhibitor, per thousand barrels of gasoline, about 1.2 pounds of N-N-disalicylidene-l.Z-diaminopropane, a metal deactivator, per thousand barrels of gasoline, and about 1.1 pounds of lecithin, a tetraethyl lead stabilizer, per thousand barrels of gasoline.
  • the improved motor fuel used in the road tests was made by incorporating in the above reference fuel an extra 0.5 theory of ethylene bromide and 0.5 percent by volume of a two-component additive comprising 0.057 pound of ester-type wax oxidate derived by catalytic oxidation of macrocrystalline wax isolated from a lubricating oil distillate of SAE 20 grade and having a neut. no. of 80, a sap. no. of 230 and an unsaponifiable content of 33 percent in a gallon of mixed naphthene-paratfin base lubricating oil having an SUS viscosity at 100 F. of about 100.
  • the weight concentrations of the oxidate and lubricating oil in the finished gasoline were respectively 0.005 and 0.6 weight percent and the tetraethyl lead scavenger mixture comprised 1.0 theory ethylene chloride and 1.0 theory ethylene bromide.
  • Cars A and B are 1955 Buicks.
  • Car A was run on the reference fuel previously described containing 0.6 Weight percent mixed base lubricating oil and 0.005 weight percent ester-type wax oxidate previously described.
  • Car B was operated on a gasoline comprising the reference fuel containing 0.5 extra theory ethylene bromide, 0.6 weight percent mixed base lubricating oil, and 0.005 weight percent ester-type oxidate.
  • Octane requirement increase of engines in service is a problem that has become more severe with the modern high compression engines.
  • An engine which has an initial octane requirement of often will develop a need for a octane fuel during service. It has been postulated that octane requirement increase is attributable partially to engine design and partially to the fuel and lubricant.
  • Octane requirement of the engine was determined approximately every 24 hours. Before taking octane requirement the oil level was checked and necessary additions made and the following items determined and recorded:
  • a modified Model H-2 Lauson engine which is a single cylinder, liquid cooled, four-stroke spark ignition engine with a bore of 2% inches and a stroke of 2% inches giving a displacement of 14.89 cubic inches, was used. Power output was rated at 4.3 H.P. at 2400 r.p.m. Compression ratio of the engine was 6.5:1 using a modified head.
  • the original flywheel magneto was replaced with a Bendix- Scintella magneto, Type CBR-4R, and coupled to the forward end of the engine crankshaft to provide ignition.
  • the engine was operated under the following conditions:
  • Test duration App. 200 hr. to equilibrium octane requirement.
  • the octane requirement of the engine was determined with primary reference fuels on the clean engine and after each period of operation until equilibrium octane requirement was attained.
  • the difference between the initial (clean) octane requirement and the equilibrium octane requirement is known as the octane requirement increase or ORI.
  • Fuel 1 was the reference fuel previously described containing 2.74 cc. per gallon of tetraethyl lead containing 1.0 theory ethylene chloride and 0.5 theory ethylene bromide.
  • Fuel 2 was this reference fuel plus 0.6 weight percent naphthene base oil and 0.005 weight percent ester-type wax oxidate previously described.
  • Fuel 3 was the leaded reference fuel plus 0.5 excess theory ethylene bromide, that is, containing 2.74 ml. per gallon of tetraethyl lead containing 1.0 theory ethylene chloride and 1.0 theory ethylene bromide.
  • Fuel 4 was the fuel of this invention comprising the reference fuel with 0.5 extra theory ethylene bromide plus 0.6 weight percent naphthene base oil and 0.005 weight percent ester-type wax oxidate previously described.
  • Table V there are shown the results in the Lauson ORI test using a lower concentration of excess ethylene bromide in conjunction with the light distillate oil-ester type oxidate combination.
  • the reference fuel in this run was a high quality premium grade fuel similar to that previously employed; the fuel had a 95 ASTM research octane ratingand contained 2.90 ml. per gallon of tetraethyl lead containing 1.0 theory ethylene chloride and 0.5 theory ethylene bromide.
  • This reference fuel had similar tests to that specified for the reference fuel employed in the road test and had a similar additive combination of gum inhibitor, lead stabilizer and metal deactivator.
  • the three-component additive of this invention comprising tetraethyl lead containing 1.0 theory ethylene chloride, 0.55 to 1.0 theory ethylene bromide, light distillate lubricating oil and a hydrocarbon oxidate which is either an ester-type oxidate or a paraffinic lubricating oil oxidate, has been shown in the foregoing extensive tests to lend many superior qualities to motor fuels. These additives mark a substantial advance in the motor fuel art.
  • An improved gasoline containing 0.2 to 1.0 weight percent of a light distillate lubricating oil fraction having an SUS viscosity at 100 F. between 50 and 300, 0.002 to 0.015 weight percent of a hydrocarbon oxidate material selected from the group consisting of an estertype oxidate derived from deoiled macrocrystalline wax having a neut. No. between 60 and 100, a sap. No. above 200, a neut. No. to sap. No. ratio between 0.25 and 0.5 and an unsaponifiable content less than 40 percent and a paraflinic lubricating'oil oxidate having a neut. No. between 55 and 80, a sap. No.
  • an unsaponifiable content less than 55 percent a viscosity less than 200 SUS at 210 F. and a Lovibond /2 cell color rating less than 200, 1-3 ml. per gallon of tetraethyl lead and a scavenger mixture comprising 1.0 theory ethylene chloride and 0.55 to 1.0 theory ethylene bromide.

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  • Oil, Petroleum & Natural Gas (AREA)
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Description

United States Patent 3,031,279 MOTOR FUEL Stanley R. Newman, Fishkill, Herbert E. Vermillion,
Wappingers Falls, Bruce S. Bailey, Fishkill, and Norman Alpert, Ponghkeepsie, N.Y., assignors to Texaco Inc., a corporation of Delaware No Drawing. Filed Feb. 16, 1959, Ser. No. 793,278 8 Claims. (Cl. 44-58) This invention relates to an improved motor fuel characterized by a plurality of improved properties. More particularly, it involves the discovery that a three-component additive comprising a light distillate lubricating oil, a hydrocarbon oxidate, and a tetraethyl lead mixture containing a prescribed amount of excess ethylene bromide is outstanding as a motor fuel additive for reducing combustion chamber deposits and their side effects, particularly preignition and octane requirement increase.
In a coassigned copending application, Serial No. 427,660, filed May 4, 1954, by R. L. Sawyer and H. E. Vermillion, now abandoned, there is disclosed a superior motor fuel containing 0.2 to 1.0 weight percent of a light distillate lubricating oil and 0.002 to 0.01 Weight percent of an ester-type wax oxidate having a neut. no. between 60 and 100, a sap. no. above 200, a neut. no. to sap. no. ratio between 0.25 and 0.4 and an unsaponifiable content less than 40 percent. The two-component additive mixture was shown to impart to a motor 'fuel the following advantages: improved road octane, anti-rust and antistalling properties, reduced engine wear, improved valve performance and life, reduced preignition, reduced induction system deposits, better fuel economy, reduced spark plug fouling and improved octane requirement increase.
In coassigned Serial No. 793,271, now US. 2,965,458, filed of even date as a continuation-in-part of the aforeidentified Serial No. 427,660, it is disclosed that a paraflinic oil oxidate having a neutralization between 60 and 70, a sap. no. between 120 and 165, a viscosity less than 100 SUS at 210 F., a Lovibond /2" cell color rating less than 100 and obtained by air oxidation of a refined paratlin base lubricating oil having an SUS viscosity between 140 and 180 at 100 F., a pour point less than 5 F. and an aniline point between 215 and 225 F., can be substituted for the ester-type wax oxidate in the twocomponent additive mixture described in the previous paragraph with equivalent results from the standpoint of gasoline performance.
The subject invention involves the discovery that the combination of the light distillate oil-hydrocarbon oil oxidate with a tetraethyl lead mixture containing a prescribed amount of excess ethylene bromide yields a superior motor fuel from the standpoint of reduced engine deposits.
The superior motor fuel of this invention contains (1) 0.2 to 1.0 weight percent of a light distillate mineral lubricating oil fraction having an SUS viscosity at 100 F. between 50 and 300, (2) 0.002 to 0.015 weight percent of a hydrocarbon oxidate which is either an ester-type oxidate derived from deoiled macrocrystalline wax having a neutralization (neut.) no. between 60 and 100, a saponification (sap.) no. above 170, a neut. no. to sap. no. ratio between 0.25 and 0.5 and an unsaponifiable content less than 40 percent, or a paraffinic lubricating oil oxidate having a neut. no. between 55 and 80 and a sap. no. between 100 and 200 and an unsaponifiable content less than about 55 percent and (3) tetraethyl lead containing a scavenger mixture consisting of 1.0 theory ethylene chloride and 0.55 to 1.0 theory ethylene bromide, theory denoting the stoichiometric amount required for reaction with the lead content of the tetraethyl lead. The ethylene bromide content of the tetraethyl lead employed in the motor fuel'of this invention is 0.05 to 0.5
ice
theory in excess of that present in the issued commercial product.
All 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, the commercial product, consists of tetraethyl lead, 1.0 theory ethylene chloride and 0.5 theory ethylene bromide, theory denoting the stoichiometric amount required for reaction with the lead content of the tetraethyl lead.
The light lubricating oil component may be a naphthene base distillate, a parafiin base distillate or mixtures thereof, but must have a low carbon residue and an SUS viscosity at F. between 50 and 300. A distillate lubricating oil fraction of this type is obtained by vacuum distillation of a naphthene, paraflin or mixed base lubrieating oil at approximately 20 to 40 mm. pressure and subsequent acid treatment of the distillate. The lubricating oil component generally used has an SUS viscosity at 100 F. of about 100. The light lubricating oil component of the additive mixture should have a Conradson carbon content below 0.02 percent and a viscosity within the prescribed range in order for the gasoline to show best results from the standpoint of engine cleanliness.
The lubricating oil component constitutes 0.2 to 1.0 weight percent of the finished gasoline of this invention. The preferred concentration of this component is in the range of 0.3 to 0.8 weight percent, with approximately 0.6 weight percent usually employed. A concentration of 0.6 weight percent is obtained by adding to gasoline about 0.5 percent by volume of a lubricating oil fraction having an SUS viscosity at 100 F. of about 100.
The ester-type wax oxidate component obtained by air oxidation of deoiled macrocrystalline wax is the product which is described in detail in the commonly assigned copending application, Serial No. 712,073, now US. 2,894,970, filed January 30, 1958, as a continuation-inpart of Serial No. 427,653, now abandoned filed May 4, 1954, in the names of I. K. McKinley, R. F. Nelson and G. S. Bright. The ester-type oxidate has a neut. no. of 60 to 100, a sap. no. above 170 and a neut. no to sap. no. ratio between 0.25 and 0.5 and preferably between 0.3 and 0.4. The ester type wax oxidate is obtained by air oxidation of a deoiled macrocrystalline wax containing less than 5 percent oil and 20 to 33 carbon atoms per molecule at a temperature between 300 and 350 F., a
pressure below 25 p.s.i.g. and an air velocity of 1.5 to 6- feet per second, equivalent to an air feed rate of 8 to 35 cubic feet of air per pound of wax per hour.
An ester-type oxidate which has given superior results in the motor fuel of this invention has been prepared from a to 127 F. melting point and semi-refined paraflin wax separated from a distillate oil of about SAE 20 grade and having about 25 to 30 carbon atoms per molecule. The 125 to 127 F. melting point wax, which contains about 0.2 to 0.4 percent oil, is separated from the distillate oil by solvent dewaxing with a solvent such as methyl ethyl ketone-toluene mixture. The con' ditions employed in the oxidation of this particularly effective oxidate are a temperature of about 330 F,
atmospheric pressure, an air velocity of 3 feet per second, equivalent in plant operation to an air feed rate of about 12.5 cubic feet of air per pound of wax per hour, and the use of a potassium permanganate catalyst. This ester-type wax oxidate has a neut. no. of about 80, a sap. no. of about 230, a neut. no. to sap. no. ratio of about 0.38 and an unsaponifiable content of about 33 percent.
The parafiinic oil oxidate component obtained by catalytic air oxidation of a refined parafiin base lubricating oil is the product described in detail in the commonly assigned copending application Serial No. 710,856, now US. Patent No. 2,978,472, filed January 24, 1958, in the names of George B. Kirkwood and John H. Greene. The parafiinic oil oxidate has a neut. 110. between 55 and 80, a sap. no. between about 100 and 200, an unsaponifiable content less than about 55 percent, a viscosity less than 200 Saybolt Universal seconds (SUS) at 210 F., a color rating less than 200 in the Lovibond /2 cell, and a pour point less than 30 F. The preferred liquid oxidates of this invention have a neut. no. between 60 and 70, a sap. no. between 120 and 165, an unsaponifiable contact less than 55 percent, a viscosity less than 100 SUS at 210 F., a Lovibond /2" cell color rating of less than 100 and a pour point less than about 10 F.
The paraffin oil oxidate is obtained by reacting a refined paraflinic lubricating oil having a viscosity of between 90 and'350 SUS at 100 F., preferably between 140 and 180 SUS at 100 F., a pour point less than 10 F., preferably less than 5 F., a Lovibond /2 cell color rating of less than and an aniline point between 210-230 F preferably between 215 and 225 F. with air in the presence of a metalliferous oxidation catalyst in a catalytic amount, e.g., between about 0.1 and 2 percent by weight of the charge oil, at an air feed rate of about 8-50 cu. ft./lb. oil/hr., at an air velocity of about 0.1 to 6 ft./sec. in an oxidation temperature range of about 250-400 F. and at a pressure of about 30-300 lbs. per square inch gauge (p.s.i.g.). The preferred conditions are an air feed rate of 1025 cu. ft./lb. oil/hr., an air velocity of about 0.2 to 1 ft./sec., an oxidation initiation temperature of 330-370 F., an oxidation reaction temperature of 260300 F., 50-90 p.s.i.g. and potassium permanganate catalyst in an amount of about 0.4 to 1.2 percent by weight of the charge oil, more preferably in the range of about 1 to 1.2 percent. The oxidation is continued until the oil is oxidized to a neut. no. between about 55 and 80, preferably between 60 and 70. Approximately between 1-6 hours reaction time is necessary to arrive at a neut. no. in the specified range.
When the oxidation step is completed, the liquid oxidate is rapidly cooled to below about 200 F. prior to removal from the reactor at a cooling rate of about 5 to 50 F./ minute, preferably between about 10 to F./minute. The oxidate is then withdrawn from the reactor and filtered to remove any solids contained therein.
The oxidate constitutes a very minor portion of the fuel composition of the invention, its concentration falling within the range of 0.002 to 0.015 weight percent of the finished gasoline. The usual concentration of the oxidate material is in the neighborhood of 0.004 to 0.008 weight percent of the finished gasoline. Concentrations of oxidate in excess of 0.015 weight percent degrade the properties of the fuel particularly in the matter of the combustion chamber and intake system deposits. If the concentration is below the prescribed lower limit, the fuel does not show the improved performance characteristics.
The oxidate is usually incorporated in the motor fuel in the solution of the distillate mineral oil. The preferred concentration of oxidate is between 0.004 and 0.006 weight percent. A mixture containing a proper proportion of components is prepared by incorporating about 0.057 lb. of oxidate in a gallon of mineral oil having an SUS at 100 F. of about 100. The resulting solution which contains approximately 0.8 percent oxidate is characterized by a neut. no. of about 0.5, a pour. point of -53 R, an SUS viscosity at 100 F. of about 105 and a gravity of 22.4 API. The use of about 0.5 percent by volume of this solution to the motor fuel gives a gasoline containing approximately 0.005 percent oxidate and 0.6 percent lubricating oil.
Tetraethyl lead is present in the motor fuels of this invention. in amounts between 1 and 3 ml. per gallon. The upper limit of 3 ml. is set by Federal regulation,
While the lower limit is generally a function of the refiners need. The usual tetraethyl lead concentration falls between 2 and 3 ml. per gallon of gasoline. The scavenger mixture comprising 1.0 theory ethylene chloride and 0.55 to 1.0 theory ethylene bromide is introduced into the fuel in combination with the tetraethyl lead.
The superior performance of the improved motor fuel of this invention has been demonstrated in laboratory bench tests and in high speed and low speed road tests. The laboratory bench tests are the type usually employed to evaluate the properties of the motor fuels and will be described in more detail hereafter. A 20,000 mile road test was run at high speed temperature conditions, specifically at 65 miles per hour in two 8-hour shifts per day in the San Antonio, Texas, area; this test was designed to evaluate the performance of the motor fuel under heavy duty conditions. A 6,000 mile road test was run under low speed, low temperature, stop and go driving conditions, specifically at 35 miles per hour in three 6-hour and 20 minute shifts per day in the Steamboat Springs, Colorado, area; this test was designed to evaluate the performance of the motor fuel under normal driving conditions.
In the 20,000 mile road test, two cars of the same make and model were employed. One car was run on the improved fuel of this invention containing tetraethyl lead having 1.0 theory ethylene chloride and 0.55 to 1.0 theory ethylene bromide, a light distillate lubricating oil and an ester-type wax oxidate, and one car was run on a reference fuel. All of the cars were lubricated with a heavy duty detergent-type motor oil meeting supplement I level requirements and of SAE grade 20.
In the low-speed, 6,000 mile test, two cars of the same make were employed. One car was run on a leaded F premium grade reference fuel. The second car was run on premium grade motor fuel containing the same additive used in the high speed test. SAE 20-20W grade advanced custom-made Havoline was used to lubricate both cars in the low-speed test.
In both road tests, all engines were disassembled, all parts washed or sprayed with L-4 type cleaner, and the engines reassembled using the manufacturers specified clearances and tolerances with the exceptions which will be itemized below. All parts removed from the engines were checked visually for possible defects, and reinstalled in the engines in their original positions, unless defective.
Compression rings were weighed to they nearest milligram and gapped to the nearest 0.00025" before and after the test to determine wear. Rings were cleaned with L-4 type cleaning solution and polished with metal polish before measurements were taken.
Cylinder bores were measured to the nearest 0.00025" at the center of, the top ring at top and bottom stroke perpendicular and parallel to thecrankshaft on all cylinders before and after test.
All con-rod bearing inserts were weighed to the nearest milligram beforeandafter test to determine weight loss. All bearings were returned ,to their original positions.
Air cleaners were disassembled, thoroughly cleaned with solvent and reassembled after oiling the element or filling with new oil (if oil bath-type) of the kind used in the engine crankcase.
All cars in the 20,000 mile test were equipped with 180 F. thermostats. All cars in the 6,000 mile test were equipped'with 150 F. thermostats.
All cars in the-20,000 mile road test were given a 900 mile break-in. There was no necessity of a break-in in the 6,000 mile road test since speed did not exceed 35 mph.
The reference fuel employed in the road tests was a high quality premium grade fuel comprising mainly fluid catalytically cracked stock and straight run gasoline. The reference fuel had a ASTM research octane rating, contained 2.74 ml. per gallon of tetraethyl lead contaim ing 1.0 theory ethylene chloride and 0.5 theory ethylene bromide, had an API gravity of 60 to 65 and a boiling point range between 100 and 398 F.; the base fuel was negative in the copper corrosion test and had an oxidation stability in the ASTM test of 240 minutes minimum. The reference fuel also contained minor amounts of conventional gasoline inhibitors, for example, approximately 6 pounds of N-N'-disecondary butyl-p-phenylenediamine, a gum inhibitor, per thousand barrels of gasoline, about 1.2 pounds of N-N-disalicylidene-l.Z-diaminopropane, a metal deactivator, per thousand barrels of gasoline, and about 1.1 pounds of lecithin, a tetraethyl lead stabilizer, per thousand barrels of gasoline.
The improved motor fuel used in the road tests was made by incorporating in the above reference fuel an extra 0.5 theory of ethylene bromide and 0.5 percent by volume of a two-component additive comprising 0.057 pound of ester-type wax oxidate derived by catalytic oxidation of macrocrystalline wax isolated from a lubricating oil distillate of SAE 20 grade and having a neut. no. of 80, a sap. no. of 230 and an unsaponifiable content of 33 percent in a gallon of mixed naphthene-paratfin base lubricating oil having an SUS viscosity at 100 F. of about 100. The weight concentrations of the oxidate and lubricating oil in the finished gasoline were respectively 0.005 and 0.6 weight percent and the tetraethyl lead scavenger mixture comprised 1.0 theory ethylene chloride and 1.0 theory ethylene bromide.
The results of the 20,000 mile road test are shown in Table I. Evaluation of' the various engine components was made by a rating system similar to the CRC L-4-545 test used for evaluating pistons and described in detail on page 401 of the CRC Handbook, 1946 edition, under the heading Oxidation Characteristics of Heavy Duty Motor Oils. This merit system involves visual examination of the engine part in question and rating them according to deposits by comparison with standards which have been assigned ratings. The rating of 10 is optimum and the rating of represents the worst condition.
Cars A and B are 1955 Buicks. Car A was run on the reference fuel previously described containing 0.6 Weight percent mixed base lubricating oil and 0.005 weight percent ester-type wax oxidate previously described. Car B was operated on a gasoline comprising the reference fuel containing 0.5 extra theory ethylene bromide, 0.6 weight percent mixed base lubricating oil, and 0.005 weight percent ester-type oxidate.
TABLE I San Antomo 20,000 M lle H lgh Speed Road Test Car A B Deposits, Visual:
Intake Manifold 9.3 9. 5 Intake Port 8. 4 8. 4 Intake Valve Tulip. 5. 6 5. 8 Combustion Chamber 5. 2 4. 9 Spark Plug Deposits 6.6 7. 2 Exhaust Valve Tulip 6.4 5. 5 Exhaust Valve Face. 7. 8 7. 2 Piston Skirts 7. 1 7. 5 ORI: 7
Before Break-In 84 87. 5 After Break-In 86. 5 88 3, 200 iles 89 88 12,800 miles 91 90. 5 20,000 miles 90 92 The results in Table I show that excellent engine cleanliness and reduced octane requirement increase result from the use of fuel containing the three-component additive of this invention. The results were somewhat better than with the two-component lubricating oil-ester type oxidate additive which is an outstanding additive in these respects as shown in the afore-identi-fied Serial No. 427,660.
In Table II there are shown the results of the low temperature 6, 000 mile road test. In the low speed test two 1955 model Cadillacs were employed. Car C used the reference fuel and Car D used the fuel of this invention employed by Car B in the results shown in Table I.
TABLE II Steamboat Springs 6,000 Mile Low Speed Road Test The data in Table II clearly show that a motor fuel containing the additive of this invention is outstanding from the standpoint of engine cleanliness and reduced octane requirement increase. The engine operated on the motor fuel of the invention had better engine ratings than the fuel containing the two-component additive. Particularly significant is the fact that the octane requirement increase of the engine operated on the motor fuel of this invention was only 2 octanes after 6,000 miles whereas the octane requirement increase of the engine operated on the two-component containing fuel was 8 octanes after a similar number of miles.
Octane requirement increase of engines in service is a problem that has become more severe with the modern high compression engines. An engine which has an initial octane requirement of often will develop a need for a octane fuel during service. It has been postulated that octane requirement increase is attributable partially to engine design and partially to the fuel and lubricant.
Reduced octane requirement increase was demonstrated in the laboratory for the additive-containing motor fuel of this invention in comparison with the reference fuel by the following procedure:
LAUSON 11-2 0R1 TEST PROCEDURE Test operation-The engine was operated under the following standard operating conditions and the data recorded as outlined in the following table:
Octane requirement of the engine was determined approximately every 24 hours. Before taking octane requirement the oil level was checked and necessary additions made and the following items determined and recorded:
Compression pressure at operating throttle position Air temperature, F.
Barometer reading, in. Hg
Spark advance, B.T.D.C. (should be 20") Amount of oil added Equilibrium octane requirement was reached when the engine had operated for 50 hours with a change in ORI of 2 numbers or less.
A modified Model H-2 Lauson engine, which is a single cylinder, liquid cooled, four-stroke spark ignition engine with a bore of 2% inches and a stroke of 2% inches giving a displacement of 14.89 cubic inches, was used. Power output was rated at 4.3 H.P. at 2400 r.p.m. Compression ratio of the engine was 6.5:1 using a modified head. The original flywheel magneto was replaced with a Bendix- Scintella magneto, Type CBR-4R, and coupled to the forward end of the engine crankshaft to provide ignition. The engine was operated under the following conditions:
Engine speed 1800 rpm.
Engine load 1600 watts.
Spark advance 20 B.T.C.
Fuel flow rate 1.6#/hr.
Air-fuel ratio 13.5 :1.
Coolant temperature 210 F.
Carburetor air temperature 100 F.
Oil temperature 175 F.
Test duration App. 200 hr. to equilibrium octane requirement.
The octane requirement of the engine was determined with primary reference fuels on the clean engine and after each period of operation until equilibrium octane requirement was attained. The difference between the initial (clean) octane requirement and the equilibrium octane requirement is known as the octane requirement increase or ORI.
The reduced octane requirement increase resulting from operating an engine with the motor fuel of this invention is shown in Table IV. In this series of runs, four different fuels were employed. Fuel 1 was the reference fuel previously described containing 2.74 cc. per gallon of tetraethyl lead containing 1.0 theory ethylene chloride and 0.5 theory ethylene bromide. Fuel 2 was this reference fuel plus 0.6 weight percent naphthene base oil and 0.005 weight percent ester-type wax oxidate previously described. Fuel 3 was the leaded reference fuel plus 0.5 excess theory ethylene bromide, that is, containing 2.74 ml. per gallon of tetraethyl lead containing 1.0 theory ethylene chloride and 1.0 theory ethylene bromide. Fuel 4 was the fuel of this invention comprising the reference fuel with 0.5 extra theory ethylene bromide plus 0.6 weight percent naphthene base oil and 0.005 weight percent ester-type wax oxidate previously described.
The foregoing data indicate a definite synergistic action between the use of a specified amount of excess ethylene bromide and a mixture of light lubricating oil and estertype wax oxidate.
In Table V there are shown the results in the Lauson ORI test using a lower concentration of excess ethylene bromide in conjunction with the light distillate oil-ester type oxidate combination. The reference fuel in this run was a high quality premium grade fuel similar to that previously employed; the fuel had a 95 ASTM research octane ratingand contained 2.90 ml. per gallon of tetraethyl lead containing 1.0 theory ethylene chloride and 0.5 theory ethylene bromide. This reference fuel had similar tests to that specified for the reference fuel employed in the road test and had a similar additive combination of gum inhibitor, lead stabilizer and metal deactivator.
In Table V, fuel 5 isthe reference fuel; Fuel 6 is the TABLE V Octane Requirement IncreaseLaus0n ORI Results Fuels: Octane requirement increase 5 13.5 6 12. 7 8
The foregoing data also demonstrate that reduced octane requirement increase is obtained operating on a motor fuel containing 0.1 extra theory ethylene bromide and the lubricating oil-ester type oxidate combination.
Results similar to those described above are obtained with an additive mixture comprising tetraethyl lead, 1.0 theory ethylene chloride, 0.55 to 1.0 theory ethylene bromide, a light lubricating oil and a parafiinic oil oxidate. Reduced octane requirement increase, less preignition and an extremely clean engine are obtained using a fuel additive of this type.
The three-component additive of this invention comprising tetraethyl lead containing 1.0 theory ethylene chloride, 0.55 to 1.0 theory ethylene bromide, light distillate lubricating oil and a hydrocarbon oxidate which is either an ester-type oxidate or a paraffinic lubricating oil oxidate, has been shown in the foregoing extensive tests to lend many superior qualities to motor fuels. These additives mark a substantial advance in the motor fuel art.
The subject application of c.-i.-p. of our copending Serial No. 557,860 filed January 9, 1956, now abandoned.
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.
We claim:
1. An improved gasoline containing 0.2 to 1.0 weight percent of a light distillate lubricating oil fraction having an SUS viscosity at 100 F. between 50 and 300, 0.002 to 0.015 weight percent of a hydrocarbon oxidate material selected from the group consisting of an estertype oxidate derived from deoiled macrocrystalline wax having a neut. No. between 60 and 100, a sap. No. above 200, a neut. No. to sap. No. ratio between 0.25 and 0.5 and an unsaponifiable content less than 40 percent and a paraflinic lubricating'oil oxidate having a neut. No. between 55 and 80, a sap. No. between and 200, an unsaponifiable content less than 55 percent a viscosity less than 200 SUS at 210 F. and a Lovibond /2 cell color rating less than 200, 1-3 ml. per gallon of tetraethyl lead and a scavenger mixture comprising 1.0 theory ethylene chloride and 0.55 to 1.0 theory ethylene bromide.
2. The gasoline according to claim 1 in which said tetraethyl lead is present in a concentration between 2 and 3 ml. per gallon.
3. The gasoline according to claim 1 in which said hydrocarbon oxidate is present in a concentration between 0.004 and 0.008 Weight percent.
4. The gasoline according to claim 1 in which the concentration of said distillate lubricating oil fraction is between 0.3 and 0.8 weight percent.
5. The gasoline according to claim 1 in which said distillate lubricating oil fraction has an SUS at F. of about 100 and a Conradson carbon content of less than 0.02 percent.
6. The gasoline according to claim 1 in which said scavenger mixture comprises 1.0 theory ethylene chloride and 1.0 theory ethylene bromide.
7. The gasoline according to claim 1 in which said scavenger mixture comprises 1.0 theory ethylene chloride and 0.6 theory ethylene bromide.
8. An improved gasoline containing 0.6 weight percent distillate mineral lubricating oil fraction having an SUS viscosity at 100 F. of about 100, 0.005 Weight percent of an ester-type oxidate derived from deoiled macrocrystalline wax having a nent. No. of about 80, a sap. No. of about 230 and an unsaponifiahle content of about 33 percent, 1-3 ml. per gallon of tetraethyl lead and a scavenger mixture comprising 1.0 theory ethylene chloride and 0.55 to 1.0 theory ethylene bromide.
References Cited in the file of this patent UNITED STATES PATENTS Stryker Oct. 6, 1931 Wasson July 13, 1937 Butz et a1. May 31, 1938 Oosterhout Apr. 25, 1939 Shokal Dec. 12, 1944 Williams Jan. 23, 1945' Bartholomew Apr. 9, 1946 Andress et a1 Oct. 3, 1953 Kleinholtz Jan. 26, 1954

Claims (1)

1. AN IMPROVED GASOLINE CONTAINING 0.2 TO 1.0 WEIGHT PERCENT OF A LIGHT DISTILLATE LUBRICATING OIL FRACTION HAVING AN SUS VISCOSITY AT 100*F. BETWEEN 50 AND 300, 0.002 TO 0.015 WEIGHT PERCENT OF A HYDROCARBON OXIDATE MATERIAL SELECTED FROM THE GROUP DEOILED MACROCYSTALLINE WAX TYPE OXIDATE DERIVED FROM DEOILED MACROCRYSTALINE WAX HAVING A NEUT. NO. BETWEEN 60 AND 100, A SAP. NO. ABOVE 200, A NEUT. NO. TO SAP. NO. RATO BETWEEN 0.25 AND 0.5 AND AN UNSAPONIFIABLE CONTENT LESS THAN 40 PERCENT AND A PARAFFINIC LUBRICATING OIL OXIDATE HAVING A NEUT. NO. BETWEEN 55 AND 80, A SAP. NO. BETWEEN 80 AND 200, AN UNSAPONIFIABLE CONTENT LESS THAN 55PERCENT A VISCOSITY LESS THAN 200 SUS AT 210*F. AND A LOVIBOND 1/2" CELL COLOR RATING LESS THAN 200, 1-3ML. PER GALLON OF TETRAETHYL LEAD AND A SCAVENGER MIXTURE COMPRISING 1.0 THEORY ETHYLENE CHLORIDE AND 0.55 TO 1.0 THEORY ETHYLENE BROMIDE.
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Citations (9)

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Publication number Priority date Publication date Assignee Title
US1826439A (en) * 1927-12-21 1931-10-06 Texas Co Motor fuel
US2086589A (en) * 1933-04-20 1937-07-13 Standard Oil Dev Co Motor fuel
US2118915A (en) * 1936-09-30 1938-05-31 Sinclair Refining Co Manufacture of wax acids
US2155678A (en) * 1935-06-25 1939-04-25 Texas Co Motor fuel
US2364921A (en) * 1942-07-06 1944-12-12 Shell Dev Leaded motor fuels
US2367815A (en) * 1941-03-21 1945-01-23 Pure Oil Co Motor fuel adjuvant
US2398281A (en) * 1944-07-08 1946-04-09 Ethyl Corp Antiknock agent
US2654697A (en) * 1950-10-31 1953-10-06 Soconyvacuum Oil Company Inc Motor fuel
US2667408A (en) * 1949-10-05 1954-01-26 Sinclair Refining Co Prevention of rust

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1826439A (en) * 1927-12-21 1931-10-06 Texas Co Motor fuel
US2086589A (en) * 1933-04-20 1937-07-13 Standard Oil Dev Co Motor fuel
US2155678A (en) * 1935-06-25 1939-04-25 Texas Co Motor fuel
US2118915A (en) * 1936-09-30 1938-05-31 Sinclair Refining Co Manufacture of wax acids
US2367815A (en) * 1941-03-21 1945-01-23 Pure Oil Co Motor fuel adjuvant
US2364921A (en) * 1942-07-06 1944-12-12 Shell Dev Leaded motor fuels
US2398281A (en) * 1944-07-08 1946-04-09 Ethyl Corp Antiknock agent
US2667408A (en) * 1949-10-05 1954-01-26 Sinclair Refining Co Prevention of rust
US2654697A (en) * 1950-10-31 1953-10-06 Soconyvacuum Oil Company Inc Motor fuel

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