US3634051A - Additives for combustible fuels - Google Patents

Additives for combustible fuels Download PDF

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US3634051A
US3634051A US814817A US3634051DA US3634051A US 3634051 A US3634051 A US 3634051A US 814817 A US814817 A US 814817A US 3634051D A US3634051D A US 3634051DA US 3634051 A US3634051 A US 3634051A
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fuel
additives
additive
zirconium
fuels
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US814817A
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Walt Phillips
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Commodity Improvements 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
    • 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
    • C10L9/00Treating solid fuels to improve their combustion
    • C10L9/10Treating solid fuels to improve their combustion by using additives
    • 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
    • C10L1/12Inorganic compounds
    • C10L1/1225Inorganic compounds halogen containing 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
    • C10L1/22Organic compounds containing nitrogen
    • C10L1/222Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • C10L1/2222(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S44/00Fuel and related compositions
    • Y10S44/905Method involving added catalyst

Definitions

  • the invention relates to both inorganic metallic and organic amine additives for combustible fuels. More specifically, the invention is concerned with fuel additives that significantly increase fuel economy as well as resulting in more complete combustion and higher flame temperatures.
  • the new additives typically act as corrosion and sulfation inhibitors in a fuel mixture, thereby performing a detergent function as well as improving the combustion process.
  • the fuel additives in accordance with the invention are particularly effective when used with liquid hydrocarbon fuels, such as fuel oils, kerosene, gasoline, etc.
  • liquid hydrocarbon fuels such as fuel oils, kerosene, gasoline, etc.
  • Advantageous results may be obtained by using the additives of the invention with solid fuels such as coal and gases, including oxygen, acetylene, hydrogen, natural and coal gases.
  • the new additives have also been found effective for use in petroleum refining and refractories.
  • the invention provides fuel additives that provide a significant improvement in combustion characteristics of combustible fuels without the typical undesirable side effects. Further, the new additives are very inexpensive and are used in very small (trace) quantities.
  • the present invention is based on the discovery that certain inexpensive inorganic metallic compounds and organic amine compounds result in substantial increases in fuel economy when added to combustible fuels in trace quantities.
  • inorganic compounds of the metal zirconium including the potassium, sodium, and lithium salts when present in trace quantities in a fuel mixture can increase fuel economy from about to percent, or more.
  • potassium fluorozirconate compounds of the formula (K ZrF where y is ID or less, and particularly the pentaand hexafluorozirconates (wherein y is 5 or 6 have been found to be remarkably effective additives for hydrocarbon and other fuels.
  • the organic amine N,N,N',N'-tetramethyl-l,3-butanediamine is a very effective fuel additive, providing hydrocarbon and other fuels with improved combustion and greater economy as well as helping to keep ignition and combustion surfaces clean.
  • a very effective fuel additive typically, from 0.5 to 2 cc. of the N,N,N,N'-tetramethyl-l,3-butanediamine additive is used per l0 gallons offuel.
  • the inorganic zirconium metal compounds of the invention appear to perform as a catalyst for the combustion process, i.e., they are not consumed during combustion and can be used in a physical form not miscible with the fuel; the organic amine additives are consumed during combustion and should be added to the fuel in a form that is miscible with the fuel. Since the organic amine additives of the invention are not typically soluble in liquid hydrocarbon fuels, they are advantageously first mixed with a solvent such as alcohol before being added to the fuel.
  • the new inorganic zirconium metal and organic amine fuel additives can be utilized either independently or together in a fuel mixture for advantageous fuel economy results.
  • the new and improved inorganic zirconium fuel additives can be used in solid form or in an aqueous solution, depending on the specific application.
  • Potassium hexafluorozirconate has excellent water solubility, without recrystallization when dissolved in boiling water at about a 3 percent by weight concentration.
  • the new zirconium additives typically function as a catalyst for hydrocarbon fuels, it is not essential to use them in solution or for them to be soluble with the fuel.
  • the new zirconium additives can be injected directly into the combustion chamber of a furnace burning a hydrocarbon fuel. When so injected, the 3 percent by weight solution can be diluted to an active ingredient concentration of l/ l 0 of 1 percent by weight.
  • the aqueous solution form of the new zirconium additives can also be used to improve the fuel economy of coal by directly spraying the aqueous solution over the coal.
  • the solid zirconium additives of the invention may be blended with powdered solid coal.
  • the optimum quantity of zirconium compound additive according to the invention is approximately /6 to 1 gram per 18 to 20 gallons of liquid fuel.
  • an equivalent amount of the zirconium additive based on the relative heat value for the solid fuels should be utilized.
  • an equivalent amount of additive should be used per equivalent B.t.u. value of the fuel.
  • EXAMPLE I About /2 to 1 gram of potassium hexafluorozirconate was placed in an ordinary household gas burner so that the natural gas (as supplied by the public utilities company) contacted the zirconium compound immediately before combustion.
  • EXAMPLE 3 An equal part by volume mixture of N, N, N, N'-tetramethyl-1,3-butanediamine and ZOO-proof ethanol was prepared. Two cubic centimeters of the mixture was added per 10 gallons of gasoline. A Volkswagen sedan, when run under highway conditions at a constant 50 m.p.h., was observed to provide a fuel economy of 40 miles per gallon of fuel mixture. The same automobile, when operated under the same conditions using the same gasoline without the amine additive of the invention, was consistently observed to have a fuel consumption rate of27 miles per gallon.
  • the new and improved inorganic zirconium compound fuel additives may be utilized with compressed gases such as oxygen, acetylene, and hydrogen, and other gases. ln gaseous applications, a trace quantity of the zirconium compound can be placed within the tank of compressed gas such that when the gas is released it passes over the zirconium compound.
  • the new and improved fuel additives can be mixed with the refractory material, e.g., porcelain, asbestos, coral, or any other suitable material, before it is placed in the refining tower.
  • the zirconium additives of the invention enhance fuel economy is not presently known, it has been observed that the inorganic zirconium additives are not consumed in the fuel combustion process and apparently act as a catalytic agent in the combustion process. it is believed that the new zirconium additives cause atomic and/or molecular changes in fuels they contact, resulting in the generation of more heat per unit of fuel and therefore requiring the consumption of less fuel for the generation of a given amount of heat.
  • the new zirconium fuel additives of the invention are used in trace quantities and are not consumed in the combustion process, their use is extremely economical and justifiable in practically any application utilizing a combustible fuel.
  • potassium hexafluorozirconate K ZrF has been found to be the most economical of the new zirconium metal additives
  • potassium pentafluorozirconate K ZrF although substantially more expensive than the hexafluoro compound, should give comparable fuel economy results.
  • composition comprising a combustible solid or liquid hydrocarbon fuel and an effective trace amount of an additive to increase fuel economy selected from the group consisting of K ZrF and K ZrF 2.
  • composition of claim 6 wherein said fuel is gasoline and said amount is from about 0.5 cc. to about 2 cc. per l0 gallons of fuel.

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

Abstract

Fuel additives that substantially improve the combustion characteristics and economy of combustible fuels when present in trace quantities are disclosed. The new additives include inorganic zirconium compounds and organic amines.

Description

United States Patent Inventor Walt Phillips Newark, NJ.
Appl. No. 814,817
Filed Apr. 9, 1969 Patented Jan. 11,1972
Assignee Commodity Improvements Inc.
New York, N.Y.
ADDITIVES FOR COMBUSTIBLE FUELS 7 Claims, No Drawings US. Cl Y 44/51,
Int. Cl C101 1/22, C101 l/l2,Cl0l 9/10 Field of Search 44/51, 68,
68 v, 72, 4, 6, 67; 252/389; 48/196EM, 197 FM, 199 FM; 260/583 P Primary ExaminerDaniel E. Wyman Assistant Examiner-W. J. Shine Attorney-Kenyon & Kenyon Reilly Carr & Chapin ABSTRACT: Fuel additives that substantially improve the combustion characteristics and economy of combustible fuels when present in trace quantities are disclosed. The new additives include inorganic zirconium compounds and organic amines.
ADDITIVES FOR COMBUSTIBLE FUELS BACKGROUND OF THE INVENTION The invention relates to both inorganic metallic and organic amine additives for combustible fuels. More specifically, the invention is concerned with fuel additives that significantly increase fuel economy as well as resulting in more complete combustion and higher flame temperatures. In addition, the new additives typically act as corrosion and sulfation inhibitors in a fuel mixture, thereby performing a detergent function as well as improving the combustion process.
The fuel additives in accordance with the invention are particularly effective when used with liquid hydrocarbon fuels, such as fuel oils, kerosene, gasoline, etc. Advantageous results may be obtained by using the additives of the invention with solid fuels such as coal and gases, including oxygen, acetylene, hydrogen, natural and coal gases. The new additives have also been found effective for use in petroleum refining and refractories.
A considerable variety of substances, such as manganese dioxide, for example, have been heretofore used as additives for improving the combustion and economy of fuels. However, the improvement in fuel economy obtainable with known additives has been very moderate and, typically, obtainable only with undesirable side effects such as unburnable deposits and corrosion.
The invention provides fuel additives that provide a significant improvement in combustion characteristics of combustible fuels without the typical undesirable side effects. Further, the new additives are very inexpensive and are used in very small (trace) quantities.
SUMMARY OF THE INVENTION The present invention is based on the discovery that certain inexpensive inorganic metallic compounds and organic amine compounds result in substantial increases in fuel economy when added to combustible fuels in trace quantities.
In accordance with the invention, inorganic compounds of the metal zirconium, including the potassium, sodium, and lithium salts when present in trace quantities in a fuel mixture can increase fuel economy from about to percent, or more.
In accordance with a specific aspect of the invention, it has been discovered that potassium fluorozirconate compounds of the formula (K ZrF where y is ID or less, and particularly the pentaand hexafluorozirconates (wherein y is 5 or 6 have been found to be remarkably effective additives for hydrocarbon and other fuels.
Additionally, it has been discovered that the organic amine N,N,N',N'-tetramethyl-l,3-butanediamine is a very effective fuel additive, providing hydrocarbon and other fuels with improved combustion and greater economy as well as helping to keep ignition and combustion surfaces clean. Typically, from 0.5 to 2 cc. of the N,N,N,N'-tetramethyl-l,3-butanediamine additive is used per l0 gallons offuel.
While the inorganic zirconium metal compounds of the invention appear to perform as a catalyst for the combustion process, i.e., they are not consumed during combustion and can be used in a physical form not miscible with the fuel; the organic amine additives are consumed during combustion and should be added to the fuel in a form that is miscible with the fuel. Since the organic amine additives of the invention are not typically soluble in liquid hydrocarbon fuels, they are advantageously first mixed with a solvent such as alcohol before being added to the fuel.
In accordance with the invention, the new inorganic zirconium metal and organic amine fuel additives can be utilized either independently or together in a fuel mixture for advantageous fuel economy results.
DESCRIPTION OF PREFERRED EMBODIMENTS The new and improved inorganic zirconium fuel additives can be used in solid form or in an aqueous solution, depending on the specific application. Potassium hexafluorozirconate has excellent water solubility, without recrystallization when dissolved in boiling water at about a 3 percent by weight concentration. However, since the new zirconium additives typically function as a catalyst for hydrocarbon fuels, it is not essential to use them in solution or for them to be soluble with the fuel.
In the form of an aqueous solution (3 percent by weight K ZrF the new zirconium additives can be injected directly into the combustion chamber of a furnace burning a hydrocarbon fuel. When so injected, the 3 percent by weight solution can be diluted to an active ingredient concentration of l/ l 0 of 1 percent by weight.
The aqueous solution form of the new zirconium additives can also be used to improve the fuel economy of coal by directly spraying the aqueous solution over the coal. Alternatively, the solid zirconium additives of the invention may be blended with powdered solid coal.
The optimum quantity of zirconium compound additive according to the invention is approximately /6 to 1 gram per 18 to 20 gallons of liquid fuel. For solid fuels such as coal, an equivalent amount of the zirconium additive based on the relative heat value for the solid fuels, should be utilized. For all fuels, generally, an equivalent amount of additive should be used per equivalent B.t.u. value of the fuel.
The following examples are supplied to illustrate the advantageous results obtainable by applying the principles of the invention.
EXAMPLE I About /2 to 1 gram of potassium hexafluorozirconate was placed in an ordinary household gas burner so that the natural gas (as supplied by the public utilities company) contacted the zirconium compound immediately before combustion.
Eight ounces of water was heated to a boil on the gas burner both with and without the zirconium compound in place.
It was observed that the water consistently reached its boiling point in 12 percent less time when the natural gas contacted the zirconium compound in the burner prior to combustion.
EXAMPLE 2 Oil burner tests utilizing trace amounts of potassium hexafluorozirconate with number 2 and number 4 fuel oil have resulted in a substantial increase in burner temperature. The amount of fuel consumed in trials wherein the zirconium compounds was present and absent was the same since the nozzle used was consistently the same. Further, the air, fuel ratio was maintained at a constant value between trial runs with and without the zirconium additive. For the oil burner tests, potassium hexaflurozirconate was added to the oil supply tank in amounts ranging from about one-half to 1 gram per 20 gallons of fuel.
The results of these oil burner tests have shown that, with all the other variables being equal, the burner temperature is consistently from between 5 and 12 percent higher when trace amounts of potassium hexafluorozirconate are present in the fuel mixture than when the zirconium compound additive is absent. Consequently, a lesser amount of fuel would be consumed to produce a given number of B.t.u.'s when trace amounts of the zirconium additives are present in the fuel oil tank.
EXAMPLE 3 An equal part by volume mixture of N, N, N, N'-tetramethyl-1,3-butanediamine and ZOO-proof ethanol was prepared. Two cubic centimeters of the mixture was added per 10 gallons of gasoline. A Volkswagen sedan, when run under highway conditions at a constant 50 m.p.h., was observed to provide a fuel economy of 40 miles per gallon of fuel mixture. The same automobile, when operated under the same conditions using the same gasoline without the amine additive of the invention, was consistently observed to have a fuel consumption rate of27 miles per gallon.
In accordance with the invention, the new and improved inorganic zirconium compound fuel additives may be utilized with compressed gases such as oxygen, acetylene, and hydrogen, and other gases. ln gaseous applications, a trace quantity of the zirconium compound can be placed within the tank of compressed gas such that when the gas is released it passes over the zirconium compound In petroleum-refining applications, the new and improved fuel additives can be mixed with the refractory material, e.g., porcelain, asbestos, coral, or any other suitable material, before it is placed in the refining tower.
Although the actual mechanism by which the zirconium additives of the invention enhance fuel economy is not presently known, it has been observed that the inorganic zirconium additives are not consumed in the fuel combustion process and apparently act as a catalytic agent in the combustion process. it is believed that the new zirconium additives cause atomic and/or molecular changes in fuels they contact, resulting in the generation of more heat per unit of fuel and therefore requiring the consumption of less fuel for the generation of a given amount of heat.
Since the new zirconium fuel additives of the invention are used in trace quantities and are not consumed in the combustion process, their use is extremely economical and justifiable in practically any application utilizing a combustible fuel. Although, at present, potassium hexafluorozirconate (K ZrF has been found to be the most economical of the new zirconium metal additives, potassium pentafluorozirconate (K ZrF although substantially more expensive than the hexafluoro compound, should give comparable fuel economy results.
It should be understood, of course, that the specific examples described herein are intended to be representative only, as certain changes may be made therein without departing from the clear teachings of the disclosure. Accordingly, reference should be made to the following appended claims in determining the full scope of the invention.
lclaim:
l. The composition comprising a combustible solid or liquid hydrocarbon fuel and an effective trace amount of an additive to increase fuel economy selected from the group consisting of K ZrF and K ZrF 2. The composition of claim 1 wherein said fuel is a fuel oil.
3. The composition of claim I wherein said fuel is a liquid hydrocarbon fuel, said additive is K ZrF and said amount is about be to l g. ofadditive per l820 gallons of fuel.
4. The process of increasing the fuel economy of combustible hydrocarbon fuels which comprise contacting said fuel with an effective trace amount of an additive selected from the group consisting of K ZrF and K ZrF and burning said fuel in contact with said additive, which acts as a catalyst.
5. The process of the claim 4 wherein said fuel is a natural gas and said additive is K ZrF 6. The composition comprising a combustible liquid hydrocarbon fuel and an effective trace amount of N,N,N, N-tetramethyll ,B-butanediamine to increase fuel economy.
7. The composition of claim 6 wherein said fuel is gasoline and said amount is from about 0.5 cc. to about 2 cc. per l0 gallons of fuel.

Claims (6)

  1. 2. The composition of claim 1 wherein said fuel is a fuel oil.
  2. 3. The composition of claim 1 wherein said fuel is a liquid hydrocarbon fuel, said additive is K2ZrF6 and said amount is about 1/2 to 1 g. of additive per 18-20 gallons of fuel.
  3. 4. The process of increasing the fuel economy of combustible hydrocarbon fuels which comprise contacting said fuel with an effective trace amount of an additive selected from the group consisting of K2ZrF5 and K2ZrF6 and burning said fuel in contact with said additive, which acts as a catalyst.
  4. 5. The process of the claim 4 wherein said fuel is a natural gas and sAid additive is K2ZrF6.
  5. 6. The composition comprising a combustible liquid hydrocarbon fuel and an effective trace amount of N,N,N'', N''-tetramethyl-1,3-butanediamine to increase fuel economy.
  6. 7. The composition of claim 6 wherein said fuel is gasoline and said amount is from about 0.5 cc. to about 2 cc. per 10 gallons of fuel.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4297110A (en) * 1980-03-31 1981-10-27 Exxon Research & Engineering Co. Zirconium additives for residual fuel oil
US4404002A (en) * 1981-08-25 1983-09-13 Exxon Research And Engineering Co. Zirconium additives for residual fuel oil
US5453210A (en) * 1994-01-24 1995-09-26 The Lubrizol Corporation Method of treating the products of combustion of landfill gas
US6206940B1 (en) 1999-02-12 2001-03-27 Exxon Research And Engineering Company Fuel formulations to extend the lean limit (law770)

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2014686A (en) * 1931-08-27 1935-09-17 Lubovitch Combustion of fuels
US2891850A (en) * 1955-08-08 1959-06-23 Shell Dev Gasoline compositions
US2948596A (en) * 1955-12-20 1960-08-09 Gulf Research Development Co Non-stalling gasoline fuel compositions
US2968148A (en) * 1958-04-16 1961-01-17 Gulf Research Development Co Vanadium-containing residual fuels modified with zinc and alkali metal compounds
US2979890A (en) * 1961-04-18 Residual fuels
US3031283A (en) * 1959-01-27 1962-04-24 Socony Mobil Oil Co Inc 1, 3-diaminobutane deicer
US3122429A (en) * 1959-09-04 1964-02-25 Ohio Commw Eng Co Jet or rocket fuel
US3126313A (en) * 1964-03-24 Certificate of correction
US3201353A (en) * 1960-06-14 1965-08-17 American Agricultural Chem Co Micro-inclusions and method of making same

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2979890A (en) * 1961-04-18 Residual fuels
US3126313A (en) * 1964-03-24 Certificate of correction
US2014686A (en) * 1931-08-27 1935-09-17 Lubovitch Combustion of fuels
US2891850A (en) * 1955-08-08 1959-06-23 Shell Dev Gasoline compositions
US2948596A (en) * 1955-12-20 1960-08-09 Gulf Research Development Co Non-stalling gasoline fuel compositions
US2968148A (en) * 1958-04-16 1961-01-17 Gulf Research Development Co Vanadium-containing residual fuels modified with zinc and alkali metal compounds
US3031283A (en) * 1959-01-27 1962-04-24 Socony Mobil Oil Co Inc 1, 3-diaminobutane deicer
US3122429A (en) * 1959-09-04 1964-02-25 Ohio Commw Eng Co Jet or rocket fuel
US3201353A (en) * 1960-06-14 1965-08-17 American Agricultural Chem Co Micro-inclusions and method of making same

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4297110A (en) * 1980-03-31 1981-10-27 Exxon Research & Engineering Co. Zirconium additives for residual fuel oil
US4404002A (en) * 1981-08-25 1983-09-13 Exxon Research And Engineering Co. Zirconium additives for residual fuel oil
US5453210A (en) * 1994-01-24 1995-09-26 The Lubrizol Corporation Method of treating the products of combustion of landfill gas
US6206940B1 (en) 1999-02-12 2001-03-27 Exxon Research And Engineering Company Fuel formulations to extend the lean limit (law770)

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