EP0279090A1 - Gasoline compositions containing hexavalent molybdenum - Google Patents

Gasoline compositions containing hexavalent molybdenum Download PDF

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Publication number
EP0279090A1
EP0279090A1 EP87301344A EP87301344A EP0279090A1 EP 0279090 A1 EP0279090 A1 EP 0279090A1 EP 87301344 A EP87301344 A EP 87301344A EP 87301344 A EP87301344 A EP 87301344A EP 0279090 A1 EP0279090 A1 EP 0279090A1
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EP
European Patent Office
Prior art keywords
molybdenum
gasoline
compound
fuel
octane requirement
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
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EP87301344A
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German (de)
French (fr)
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EP0279090B1 (en
Inventor
Paul James Cahill
Larry Charles Satek
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BP Corp North America Inc
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BP Corp North America Inc
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Priority to US06/833,225 priority Critical patent/US4647293A/en
Application filed by BP Corp North America Inc filed Critical BP Corp North America Inc
Priority to EP87301344A priority patent/EP0279090B1/en
Priority to AT87301344T priority patent/ATE69835T1/en
Priority to DE8787301344T priority patent/DE3774868D1/en
Publication of EP0279090A1 publication Critical patent/EP0279090A1/en
Application granted granted Critical
Publication of EP0279090B1 publication Critical patent/EP0279090B1/en
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00Use of additives to fuels or fires for particular purposes
    • C10L10/10Use of additives to fuels or fires for particular purposes for improving the octane number
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/18Organic compounds containing oxygen
    • C10L1/1814Chelates
    • 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
    • C10L1/1828Salts 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
    • C10L1/188Carboxylic 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
    • C10L1/24Organic compounds containing sulfur, selenium and/or tellurium
    • C10L1/2431Organic compounds containing sulfur, selenium and/or tellurium sulfur bond to oxygen, e.g. sulfones, sulfoxides
    • C10L1/2437Sulfonic acids; Derivatives thereof, e.g. sulfonamides, sulfosuccinic 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
    • C10L1/26Organic compounds containing phosphorus
    • C10L1/2633Organic compounds containing phosphorus phosphorus bond to oxygen (no P. C. 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)

Definitions

  • This invention relates to improved unleaded gaso­line compositions. More particularly, the invention relates to the incorporation of molybdenum(VI) compounds into an unleaded gasoline for the purpose of reducing elevated steady state octane requirement and suppressing octane requirement increase in spark ignition internal combustion engines.
  • a great number of gasoline additives including antiknock agents, deposit reducing agents, demulsifiers, etc., have been developed in recent years.
  • a commer­cially important antiknock agent, tetraalkyl lead has, until recently, been universally used to prevent engine knock by increasing the octane number of gaso­line.
  • broad restrictions have been placed on the use of lead in gasoline.
  • greater amounts of expensive, high octane blending stock must be used to produce gasoline having sufficient octane for current produc­tion automobiles.
  • ORI is believed to be one result of thermally insulating combustion chamber deposits formed from gasoline contaminants and from the incomplete combus­tion of gasoline and lubricating oil. Initially the rate of deposit formation is substantially greater than the rate of disintegration, and the deposits rapidly build. As the deposits thicken, the rate of disintegration approaches and eventually equals the rate of formation. At this point, the deposits reach a steady state thickness. Knock in the engine appears to increase in incidence and severity as the deposit builds and reaches a constant or steady state elevated rate of incidence and severity corresponding to the steady state thickness of the deposit. At this point the engine commonly has an elevated steady state octane requirement which can be 2 to 15 research octane numbers greater than the octane requirement when new.
  • combustion chamber deposits have the substantial ability to prevent transfer of thermal energy from the combustion chamber into engine coolant, causing accumulation of thermal energy in the deposits and in the combustion chamber.
  • a spark ignites the air/fuel mixture in the combustion chamber, a flame front is initiated and combustion rapidly and smoothly progresses from the spark plug to the "end-gas region" opposite to the spark plug.
  • the high pressure flame front rapidly compresses the unburned air/fuel mixture which is at a relatively lower pressure in the end-gas region as the front progresses through the chamber.
  • the combustion progresses through the combustion chamber, and knock is not heard.
  • ORI can readily be remedied with leaded gasoline by increasing the lead concentration.
  • a greater amount of high octane blending stock must be used to increase the octane.
  • high octane blending stock commonly contains aromatic con­stituents that are more likely to leave thermally insulating deposits and increase ORI.
  • octane requirement increase shall mean the gradual increase in octane requirement observed as an engine ages.
  • Elevated steady state octane requirement shall mean the octane requirement of an engine with combustion chamber deposits that have reached a steady state both in thickness and in resistance to thermal energy flow.
  • U.S. Patent Nos. 3,615,293 and 3,755,195 disclose the incorporation of various organic molybdenum com­pounds into a gasoline fuel which contains an organo­manganese antiknock agent. These patents teach that the molybdenum compounds are effective in reducing spark plug fouling by gasoline fuels which contain organomanganese antiknock agents. It is further disclosed that suitable organic molybdenum compounds include molybdenum salts and chelates. However, these references fail to suggest the incorporation of a molybdenum compound into gasoline for any purpose in the absence of an organomanganese antiknock agent.
  • U.S. Patent No. 3,317,571 discloses the prepara­tion of organomolybdenum compounds wherein one or more molecules containing an amide or thioamide linkage are bonded to the molybdenum atom through a sulfur or oxygen linkage and which is stabilized by additional covalent bonding to a plurality of carbonyl groups.
  • This patent discloses that such compounds can be used in gasoline, either alone or in combination with lead alkyls, as antiknock agents. It fails, however, to either teach or suggest the use of a molybdenum(VI) compound for any purpose.
  • U.S. Patent No. 3,272,606 discloses that small amounts of a covalent molybdenum polycarbonyl compound can be used in gasoline in combination with an organo­lead antiknock agent to enhance the antiknock properties of the organolead antiknock agent.
  • this reference fails to suggest the incorporation of a molybdenum compound into gasoline for any purpose in the absence of an organolead antiknock agent.
  • U.S. Patent No. 2,086,775 is directed to the incorporation of various organometallic compounds into a liquid fuel for an internal combustion engine.
  • Suitable organometallic compounds are those of cobalt, nickel, manganese, iron, copper, uranium, molybdenum, vanadium, zirconium, beryllium, platinum, palladium, thorium, chromium, aluminum, and the rare earth metals.
  • the liquid fuel may also contain an organolead antiknock agent. It is disclosed that use in an internal combustion engine of a fuel containing small amounts of these organometallic compounds results in the formation of a catalytic deposit within the combustion chambers of the engine which is effective for the elimination of knock and the improvement of combustion within the engine.
  • this patent offers no guidance for selecting a molybdenum(VI) compound for use in a gasoline composition which is substantially free of other metals for the purpose of suppressing octane requirement increase and reducing elevated steady state octane requirement in spark ignition internal combustion engines.
  • U.S. Patent No. 3,155,620 is directed to the use of cycloheptatriene transition metal coordination compounds of the Group VIB metals as additives for liquid hydrocarbon compositions.
  • This patent teaches that such additives can be used to increase the octane of liquid fuels and to provide improved lubricating properties when incorporated into lubricating oil compositions.
  • these coordination compounds can be used in combination with antiknock agents such as organolead compounds.
  • this patent fails to either teach or suggest the use of a molybdenum(VI) compound for any purpose.
  • U.S. Patent No. 3,440,028 is directed to the incorporation of a metal halide hydrocarbyl orthophos­phate additive into leaded gasoline compositions for the purpose of suppressing the tendency of the lead to increase undesirable surface ignition within the combustion chambers of an engine.
  • the metal of the additive can be selected from the group consisting of manganese and metals of Groups IB, IIA, IIB, IVA, VIB and VIII of the Periodic Table.
  • U.S. Patent No. 3,240,576 discloses that the addition to leaded gasoline of a gasoline soluble organomolybdenum com­pound will provide a substantial reduction of surface ignition in the combustion chambers of a spark ignition internal combustion engine.
  • U.S. Patent No. 3,401,184 is directed to a method for the preparation of metal organo orthophosphates wherein the metal can be selected from Groups II, IV, VI and VIII of the Periodic Table. It is disclosed that these compounds have utility as gasoline additives and that when so used they impart rust inhibition, surface ignition suppression, carburetor detergency, carburetor icing alleviation and reduction in octane requirement increase to the gasoline composition.
  • U.S. Patent No. 3,282,838 discloses the use of amine salts of chromic or molybdic acid as corrosion inhibitors in petroleum hydrocarbons such as gasoline. These amine salts contain either a chromic or molybdic ion of +6 valence and are used at a concentration level between about 0.005 and 5 weight percent.
  • U.S. Patent No. 3,003,859 discloses the incorporation into a liquid hydrocarbon, such as gaso­line, of about 0.005 to about 5 percent by weight of a metal-organic material which is obtained by heating a normally-solid metallic chelate compound formed from a beta -keto ester to a temperature above its melting point. It is further disclosed that these metal chelates can be formed from metallic elements of the Periodic Table comprising the Groups IA, IB, IIA, IIB, IIIA, IIIB, IVA, IVB, VA, VB, VIB, VIIB and VIII including the lanthanide and actinide series of rare earth elements.
  • This patent fails to offer any guidance for selecting a molybdenum(VI) compound for the purpose of suppressing octane require­ment increase and reducing elevated steady state octane requirement in spark ignition internal combustion engines.
  • the present invention is directed to the discovery that the incorporation of small amounts of a gasoline soluble molybdenum(VI) compound into unleaded gasoline affords a fuel composition which is effective in reducing elevated steady state octane requirement and suppressing octane requirement increase in spark igni­tion internal combustion engines.
  • One embodiment of the invention is a gasoline fuel composition
  • a gasoline fuel composition comprising a major proportion of a liquid hydrocarbon fuel of gasoline boiling range in combination with a molybdenum(VI) compound which is soluble in said hydrocarbon fuel, wherein the amount of said molybdenum(VI) compound is from about 0.1 to about 20.0 parts per one million parts of hydrocarbon fuel, said fuel composition is substantially free of metals other than molybdenum, and said molybdenum(VI) compound is selected from the group consisting of molybdenum(VI) sulfonates, molybdenum(VI) diamine complexes, amine salts of molybdic acid and isopoly­molybdic acid, and molybdenum(VI) compounds which are free of nitrogen, sulfur and phosphorus.
  • Another embodiment of the invention is a gasoline fuel composition
  • a gasoline fuel composition comprising a major proportion of a liquid hydrocarbon fuel of gasoline boiling range in combination with a molybdenum(VI) compound which is soluble in said liquid hydrocarbon fuel, wherein the amount of said molybdenum(VI) compound is effective to suppress octane requirement increase in a spark ignition internal combustion engine, said fuel composi­tion is substantially free of metals other than molyb­denum, and said molybdenum(VI) compound is selected from the group consisting of molybdenum(VI) sulfonates, molybdenum(VI) diamine complexes, amine salts of isopoly molybdic acid, and molybdenum(VI) compounds which are free of nitrogen, sulfur and phosphorus.
  • Another embodiment of the invention is a gasoline fuel composition
  • a gasoline fuel composition comprising a major proportion of a liquid hydrocarbon fuel of gasoline boiling range in combination with a molybdenum(VI) compound which is soluble in said liquid hydrocarbon fuel, wherein the amount of said molybdenum(VI) compound is effective to reduce elevated steady state octane requirement in a spark ignition internal combustion engine, said fuel composition is substantially free of metals other than molybdenum, and said molybdenum(VI) compound is selected from the group consisting of molybdenum(VI) sulfonates, molybdenum(VI) diamine complexes, amine salts of isopoly molybdic acid, and molybdenum(VI) compounds which are free of nitrogen, sulfur and phosphorus.
  • a further embodiment of the invention is a method for reducing elevated steady state octane requirement in a spark ignition internal combustion engine and maintaining the resulting reduced steady state octane requirement which comprises operating said engine on a first gasoline fuel composition until a reduced steady state octane requirement is achieved and main­taining said reduced steady state octane requirement by operating the engine on a second gasoline fuel composition, wherein said first fuel comprises a major proportion of a liquid hydrocarbon fuel of gasoline boiling range in combination with an amount of a soluble molybdenum(VI) compound which is sufficient to provide from about 10 to about 1000 parts of molyb­denum per million parts of liquid hydrocarbon fuel, wherein said second fuel comprises a major proportion of a liquid hydrocarbon fuel of gasoline boiling range in combination with an amount of a soluble molyb­denum(VI) compound which is sufficient to provide from about 0.01 to about 10 parts of molybdenum per million parts of liquid hydrocarbon fuel, and wherein both of said first and second fuels are substantially free
  • a further embodiment of the invention is a method for reducing elevated steady state octane requirement and/or suppressing octane requirement increase in a spark ignition internal combustion engine which comprises operating said engine with a gasoline fuel composition comprising a major proportion of a liquid hydrocarbon fuel of gasoline boiling range in combina­tion with a molybdenum(VI) compound which is soluble in said liquid hydrocarbon fuel, wherein the amount of said molybdenum (VI) compound is effective to reduce elevated steady state octane requirement and/or sup­press octane requirement increase in said engine, said fuel composition is substantially free of metals other than molybdenum, and said molybdenum (VI) compound is selected from the group consisting of molybdenum (VI) sulfonates, molybdenum (VI) diamine complexes, amine salts of molybdic acid and isopoly molybdic acid, and molybdenum (VI) compounds which are free of nitrogen, sulfur and
  • a still further embodiment of the invention is a method for reducing elevated steady state octane requirement in a spark ignition internal combustion engine having an increased octane requirement of about 2 to about 7 units after operation with gasoline substantially free of lead and molybdenum which com- prises operating said engine with a gasoline fuel composition
  • a gasoline fuel composition comprising a major proportion of a liquid hydrocarbon fuel of gasoline boiling range in combina- tion with a molybdenum (VI) compound which is soluble in said hydrocarbon fuel, wherein the amount of said molybdenum (VI) compound is sufficient to provide from about 10 to about 1000 parts of molybdenum per million parts of said hydrocarbon fuel, and the amount of said gasoline fuel composition is effective to reduce said elevated steady state octane requirement by at least about 20%.
  • the general object of this invention is to sup-­press ORI and reduce elevated steady state octane requirement arising in internal combustion engines using unleaded fuels. Another object is to modify the thermal conductivity of combustion chamber deposits to increase heat conduction and thereby reducing elevated steady state octane requirement and suppressing ORI. Still another object of the invention is to promote the formation of thermally conductive deposits in internal combustion engines. A further object of the invention is to provide low octane gasoline that can be used in an engine without harmful knock arising as the engine ages. A still further object of the invention is to increase the efficiency of gasoline production by producing more low octane gasoline from crude oil.
  • octane requirement increase and the elevated steady state octane require­ment caused by combustion chamber deposits in internal combustion engines can be prevented or reduced by operation of an internal combustion engine wherein the combustion processes in the combustion chamber are performed in the presence of a hexavalent molyb­denum, molybdenum(VI) or molybdenum +6 compound.
  • the hexavalent molybdenum compound can be provided to the combustion chamber by a gasoline substantially free of lead compounds containing a gasoline soluble hexa­valent molybdenum compound, or by a lubricating oil containing the molybdenum compound which is transported into the combustion chamber during the operation of the engine.
  • certain pre­ferred hydrocarbon soluble compounds containing molyb­denum in the +6 oxidation state that are effective in preventing octane requirement increase and are effective in reducing elevated steady state octane requirement.
  • molybdenum compounds of any oxidation state to prevent octane requirement increase and reduce elevated steady state octane requirement has been investigated by us previously.
  • molybdenum(VI) compounds serve to efficiently afford these results.
  • molybdenum(VI) compounds efficiently alter the thermal energy transfer characteristics of combustion chamber deposits so that heat can be rapidly conducted from combustion chamber to engine coolant. Since the modified deposits no longer impede efficient removal of heat from the combustion chamber, the gasoline is ignited solely by the spark and the fuel is burned uniformly in the combustion chamber, efficiently transmitting combustion energy to the road in the absence of knock, ping, loss in efficiency or mechanical damage.
  • the improved gasoline compositions of this invention can be prepared by combining with a major portion of gasoline substantially free of lead compounds an effective octane requirement increase suppressing or an effective steady state octane requirement reducing amount of a gasoline soluble compound containing molybdenum(VI), hexavalent molyb­denum, or molybdenum +6.
  • the improved lubricants of the invention can be prepared by combining with a lubricant an effective amount of a hydrocarbon soluble molybdenum(VI) compound.
  • One aspect of the invention is an unleaded gaso-­line, used in "clean,” new engines, containing a low concentration of a hydrocarbon soluble molybdenum (VI) compound comprising a major portion of gasoline and about 0.1 to about 20 parts of the molybdenum (VI) compound per one million parts of gasoline.
  • a molybdenum (VI) compound can be used in an amount which is sufficient to provide from about 0.01 to about 10 parts of molybdenum, calculated as the metal, per million parts of gasoline.
  • Another aspect of the invention is a gasoline, for use in "dirty" engines that have reached an elevated steady state octane requirement caused by deposits in the combustion chamber, to substantially reduce the elevated steady state octane requirement.
  • This composition which modifies the existing deposits and reduces the elevated steady state octane require-­ment, comprises a major portion of gasoline and about 20 to about 10,000 parts of a hydrocarbon soluble molybdenum (VI) compound per one million parts of gasoline.
  • a molybdenum (VI) com-­pound can be used in an amount which is sufficient to provide from about 10 to about 1000 parts of molybdenum, calculated as the metal, per million parts of gasoline.
  • a further aspect of the invention is a concentrate of a hydrocarbon soluble molybdenum (VI) compound con-­taining about 0.1 to about 50 wt% of the compound in a suitable diluent which can be dissolved in proper proportion in gasoline or lubricating oil to provide about 0.1 to about 10,000 parts of molybdenum (VI) compound per one million parts of gasoline or about 0.001 to about 5 wt% of molybdenbum (VI) compound in a lubricating oil.
  • a hydrocarbon soluble molybdenum (VI) compound con-­taining about 0.1 to about 50 wt% of the compound in a suitable diluent which can be dissolved in proper proportion in gasoline or lubricating oil to provide about 0.1 to about 10,000 parts of molybdenum (VI) compound per one million parts of gasoline or about 0.001 to about 5 wt% of molybdenbum (VI) compound in a lubricating oil.
  • a still further aspect of the invention is a lubricating oil containing a hydrocarbon soluble molyb­denum compound which when used to lubricate an engine provides to the combustion chamber a substantial amount of molybdenum(VI), by oxidation of a molybdenum com­pound or by other means, that can suppress ORI or reduce elevated steady state octane requirement.
  • lubricating oils contain about 0.001 to about 5 wt%; preferably about 0.01 to about 2 wt%; and most preferably, to reduce molybdenum consumption and provide maximum benefit, about 0.01 to about 1 wt% of molybdenum(VI) compound.
  • the molybdenum(VI) containing gasoline compositions of this invention are preferably substantially free of lead, more preferably substantially free of both lead and manganese, and most preferably substantially free of metals other than molybdenum.
  • any hydrocarbon soluble molybdenum(VI) compound which is stable in hydrocarbon or petroleum storage or distribution facilities can be used in gasoline in accordance with this invention.
  • the molybdenum(VI) or compound is selected from the group consisting of molybdenum(VI) sulfonates, molybdenum(VI) diamine complexes, amine salts of molybdic acid and isopoly molybdic acid, and molybdenum(VI) compounds which are free of nitrogen, sulfur and phosphorus.
  • the molybdenum(VI) compound is selected from the group consisting of molybdenum(VI) sulfonates, molybdenum(VI) diamine complexes, amine salts of isopoly molybdic acid, molybdenum(VI) carboxylates, molybdenum(VI) salts of naphthenic acids, molybdenum(VI) phenates, molybdenum(VI) alkoxides, molybdenum(VI) aryloxides, and molybdenum(VI) beta -diketone complexes.
  • phosphorus containing compounds of molybdenum(VI) can be used in the practice of this invention, they are ordinarily not preferred. This is a consequence of the fact that phosphorus is considered to be harmful to the catalytic converters which are currently employed to control the emission of hydrocarbons, carbon monoxide and nitrogen oxides from automotive engines.
  • Molybdenum compounds useful to suppress ORI or reduce elevated steady state octane requirement include a broad variety of molybdenum(VI) compositions.
  • a useful class of molybdenum(VI) compositions can be formed by the reaction of molybdenum in a variety of forms with a ligand.
  • these ligands are acetylacetone, N -nitrosophenylhydroxylamine, dimethylglyoxime, ethylenediamine, ethylenediamine­tetraacetic acid, nitrilotriacetic acid, 8-hydroxy­quinoline, benzoylacetone, 2,4-pentanediene, beta -­diketones, oxygen, halogens, Mannich products, phosphates, phosphine oxides, alkanol amines, sulfoxides formamides and other similar well known chelating agents.
  • Another useful class of hydrocarbon soluble molybdenum compositions includes molybdenum(VI) beta -­diketonates wherein the beta -diketone can be represented by the formula: At least one proton on the carbon atom between the carbonyl groups is necessary for the formation of the molybdenum complex. The removal of this proton generates a beta -diketone anion which can chelate the metal ion present.
  • R1 and R2 are hydrocarbyl groups of 1 to 50 carbon atoms and include primary, secondary and tertiary alkyl, alkenyl and aromatic groups.
  • Preferred alkyl groups are methyl, ethyl, isopropyl, t -butyl, sec -amyl, 2-ethylhexyl, eicosyl, pentacontyl, having both normal chains and branched chains.
  • R3 can be hydrogen or a hydrocarbyl group of 1 to 50 carbon atoms.
  • R3 is hydrogen or an alkyl group, for example methyl, ethyl, isopropyl, t -butyl, amyl, n -hexyl, pentacontyl, etc., having both normal and branched chain.
  • Beta -diketones are well known in the art, some are available commercially, and all are readily prepared by methods well known in the art.
  • the commonly used compounds are prepared from beta -diketones wherein R1 and R2 represent alkyl groups of 1 to 20 carbon atoms and R3 represents hydrogen. More specifically, the preferred beta -diketones are 2,4-pentanedione, 3-methyl-2,4-pentanedione, 3-isopropyl-­2,4-pentanedione, 2,4-hexanedione, 2-methyl-3,5-­hexanedione, 4-methyl-3,5-heptanedione, 3,5-heptanedione, 2,6-dimethyl-3,5-heptanedione, 2-methyl-4,6-heptanedione, 2-methyl-4,6-octanedione, 2,8-dimethyl-4,6-nonanedione, and 2,2,6,6-tetramethyl-3,5-heptanedione.
  • Other beta -­diketone complexes are discussed by Morgan and Castell
  • Another useful class of hydrocarbon soluble molybdenum(VI) complexes that can be used in the practice of this invention is composed of molybdenum(VI) diamine complexes wherein the diamine ligand is represented by: R4R5N-(CR4R5) n -NR4R5 wherein n is an integer from 1 to 20, preferably for reasons of stability of the molybdenum-amine product, n is 2 to 4.
  • the R4 and R5 substituents can be independently hydrogen or alkyl of 1 to 20 carbon atoms and the amino groups can be independently primary, secondary or tertiary groups.
  • diamines include ethylenediamine, 1,2-propylenediamine, 1,3-­ propylenediamine, 2-methyl-1,3-diaminopropane, 2,2-­dimethyl-1,3-diaminopropane, ortho -phenylenediamine and the corresponding 1 to 20 carbon alkyl-substituted diamines.
  • hydrocarbon soluble molybdenum(VI) compounds include molybdenum-polyamine Mannich complexes, molybdenum-polyamine substituted dicarboxylic acid complexes, disclosed in U.S. Serial No. 190,590, filed September 25, 1980, which is expressly incorporated by reference herein.
  • molybdenum(VI) compositions includes the neutralization products of molybdic acid including iso and heteropoly molybdic acid with an oil soluble base and the neutralization of an acid with a molybdenum base.
  • Gasoline soluble amine salts of the formula: [R6R7R8NH]2MoO4 can be used in the practice of this invention wherein R6 is a hydrocarbyl radical, and R7 and R8 are independently selected from the group consisting of hydrogen and hydrocarbyl.
  • Typical hydrocarbyl radicals include, for instance: alkyl, alkenyl, aryl, alkaryl, arylalkyl, or alicyclic radicals.
  • hydrocarbyl radicals are : methyl, ethyl, propyl, butyl, isohexyl, 2-ethylhexyl, neodecyl, dodecyl, octadecyl, eicosyl, nonacosyl, phenyl, naphthyl, benzyl, cresyl, ethylphenyl, phenylhexyl, cyclohexyl, cyclo­propyl, cyclopentyl, butenyl, octenyl, linoleyl, etc.
  • Another useful class is composed of hydrocarbon soluble molybdenum(VI) dialkyl phosphates, phosphoro­thioates and phosphorodithioates which are derived from a phosphorus containing moiety of the formula: wherein each X can be independently selected from oxygen or sulfur and each R9 is independently selected from hydrocarbon alkyl and aryl groups having from one to about 30 carbon atoms.
  • molybdenum(VI) compositions are: molybdenum-dimethylphosphorothioate molybdenum-dioctylphosphorothioate molybdenum-diphenylphosphate molybdenum-dicresylphosphate molybdenum-didecylphosphorodithioate molybdenum-diamylphosphorotetrathioate molybdenum-di- tert -butylphosphorotrithioate molybdenum-dixylylphosphorothioate molybdenum-di-4-ethylphenylphosphorotrithioate molybdenum-dioctadecylphosphorotetrathioate molybdenum-cresylphenylphosphate molybdenum-dinaphthylphosphorothioate molybdenum-diisopropylphosphorothioate molybdenum-dibenz
  • molybdenum(VI) carboxylates of this type are molybdenum pentanoate, molybdenum octanoate, molybdenum oleate, molybdenum linoleate, molybdenum adipate, molybdenum 2-ethylhexanoate, molybdenum benzoate, molybdenum tetradecanoate, molyb­denum orthophthalate, molybdenum 4-dodecylbenzoate, molybdenum stearate, molybdenum laurate and the like.
  • Molybdenum(VI) salts of mixtures of fatty acids obtained from natural products such as olive oil, tall oil, cottonseed oil, tallow, coconut oil and the like are also useful.
  • Other molybdenum(VI) compounds of this type are the salts of alicyclic carboxylic acids.
  • molybdenum(VI) salts of alicyclic carboxylic acids are molybdenum cyclopentanecarboxylate, molybdenum cyclopentylacetate, molybdenum 3-methylcyclopentylacetate, molybdenum camphoate, molybdenum cyclohexanecarboxylate, molyb­denum 3-dodecylcyclohexanecarboxylate, molybdenum 2,6-dicyclohexylcyclohexanecarboxylate, molybdenum 2-cyclohexyl-4,6-dipentyl-4-methylcyclohexanecarboxylate, molybdenum 4-methylcyclohexanecarboxylate, molybdenum 2,2,6-trimethylcyclohexanecarboxylate and the like.
  • hydrocarbon soluble molybdenum(VI) compositions which is useful in the practice of this invention are salts of the so-called naphthenic acids.
  • naphthenic acids is applied to a mixture of carboxylic acids obtained from the alkali washes of petroleum. These acids are complex mixtures of normal and branched aliphatic acids, alkyl derivatives of cyclopentane- and cyclohexane-carboxylic acids and cyclopentyl and cyclohexyl derivates of aliphatic acids. The alicyclic carboxylic acids appear to be the major constituents of these mixtures.
  • Molybdenum(VI) sulfonates wherein the sulfonate moiety has the general formula: ArSO can also be used in the practice of this invention.
  • Sulfonic acid compounds useful to prepare molybdenum(VI) sulfonates can have the following general formula: XSO3-(Ar) n -A m wherein A is hydrogen, an alkyl, or other hydrocarbyl group with hydroxy-, chloro-, or bromo-substituents; Ar is an aryl unit including benzene, naphthalene, etc.; m is an integer of 1 to 5; n is an integer of 0 to 5; and X is a halogen or hydrogen.
  • A can be any substantially hydrocarbyl or substituted hydrocarbyl group which results in a hydrocarbon benzene sulfonic acid.
  • A can be a hydrogen or a substantially aliphatic group with about 1 to 15 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, t -butyl, nonyl, decyl, dodecyl, pentadecyl and the like, with a molecular weight of about 120 and greater; an intermediate molecular weight alkyl group such as polyisobutylene or polypropylene polymers with 15 to 1,000 carbon atoms with a molecular weight of about 200 to 14,000; a high molecular weight hydrocarbyl such as polyolefin having a number average molecular weight in excess of 14,000; and others.
  • A can be substituted with groups such as chlorine, bromine, or hydroxy groups.
  • Ar can have more than one substituent, for example, alky
  • suitable oil soluble benzenesulfonic acids are the oil soluble, so-called petroleum sulfonic acids which are also commonly referred to as mahogany acids, having a molecular weight from about 350 to 750, aryl sulfonic acids, and alkaryl sulfonic acids.
  • suitable sulfonic acids are diparaffin wax-substituted phenolsulfonic acid, cetylchlorobenzene­sulfonic acid, cetylphenoldisulfidesulfonic acid, cetylphenolmonosulfidesulfonic acid, etc.
  • Other suitable oil-soluble sulfonic acids are well described in the art such as U.S. Patent Nos. 2,616,604; 2,626,207; 2,767,209; and others.
  • the inexpensive, low molecular weight polypropylbenzenesulfonic acids having a molecular weight of about 200 to 1,200 are preferred.
  • molybdenum(VI) phenates which are the reaction product of a molybdenum compound and a phenol compound.
  • useful phenol compounds include: 4-methylphenol, 4-octadecylphenol, 4-oleylphenol, 4-(2-ethyl-n-hexyl)phenol, 2,6-dimethylphenol, 2,4,6-trimethylphenol, o -chlorophenol, 2-dodecylphenol, 2,4-didodecylphenol, p -nonylphenol, 2- tert -butylphenol , 4-dodecylphenol, 4-polyisobutylene substituted phenol, and the like.
  • An especially useful type of a molybdenum(VI) phenate is that derived from a commercial mixture of alkylated phenols.
  • Commercial alkylation of phenols generally is accomplished by treating the phenol with an olefin, or polyolefin or mixtures thereof in the presence of an alkylating agent.
  • This commercial alkylation ordinarily produces a mixture of various alkyl phenols.
  • a phenol is alkylated with a C9 olefin
  • the product will contain monononyl­phenols, dinonylphenols, and trinonylphenols.
  • C9, C10, and C18 olefins is used in the alkylation, a mixture of various C9, C10, and C18 alkylated phenols is obtained.
  • Preferred hydrocarbon soluble molybdenum(VI) compounds for reasons of solubility in gasoline and lubricating oil and the substantial reduction of octane requirement increase and equilibrium octane requirement, include cis -dioxobis(dipivaloyl­methanato)molybdenum(VI), MoO2(THD)2 and trans -­dioxobis(dipivalolylmethanato)molybdenum(VI), molybdenum(VI) octoate and naphthanate, methylenebis(2-­oxo-4-dodecylphenol)molybdenum(VI), dioxo-N,N ⁇ -(2-­oxo-4-nonylbenzyl)ethylenediaminemolybdenum(VI), molybdenum(VI) sulfonate, and molybdenum(VI) polyamine-­Mannich complex comprising the reaction product of a molybdenum
  • the improved gasolines and lubricants of this invention having the ability to prevent substantial octane requirement increase and to reduce high equilibrium octane requirement are produced by combining a gasoline or a lubricating oil with an amount of a hydrocarbon soluble hexavalent molybdenum compound which is effective to reduce ele­vated steady state octane requirement and/or suppress octane requirement increase.
  • the threshold for each compound lies between about 0.01 and 3.0 parts of molybdenum per one million parts of gasoline.
  • the threshold concentration varies due to the effect on the molybdenum of the radicals or groups attached.
  • the concentration of the molybdenum can range from 0.01 to about 10 parts of molybdenum per million parts of gasoline to prevent substantial increase in octane requirement.
  • a gasoline containing about 10 to about 1000 parts of molybdenum per million parts of gasoline can be used until the steady state octane requirement has been reduced to near the "clean" octane requirement level. At that point, the concentration of the molybdenum in the gasoline can be reduced to about 0.01 to about 10.0 parts per million parts of gasoline.
  • the hydrocarbon fuels to which the molybdenum(VI) compounds can be added comprise hydrocarbons boiling in the gasoline range which range is normally about 20°C-225°C.
  • the base fuel can comprise straight-­chain or branched-chain paraffins, cycloparaffins, olefins, and aromatic compounds or any mixture of such hydrocarbons obtainable from straight-run naphtha, polymeric gasoline, natural gasoline, thermally or catalytically cracked hydrocarbon stocks, alkylate gasoline and catalytically reformed stocks.
  • the fuels can have a research octane number of about 60 to about 100 or preferably about 85 to about 95 for reason of fuel economy and engine performance.
  • the gasoline may also contain conventional gasoline additives such as nonmetallic antiknock compounds, dyes, antioxidants, anti-icing agents, rust inhibitors, detergents, anti-­preignition agents, stabilizers, intake valve deposit control additives and the like.
  • gasolines contain a carrier fluid which remains stable and fluid in the induction system and can promote induction system cleanliness by dissolving hydrocarbon soluble deposits.
  • a preferred embodiment of the invention involves the use of a minor amount of methyl t -butyl ether as an antiknock agent.
  • the molybdenum(VI) compounds are effective in lubricant compositions when used in amounts providing about 0.001 to about 5 wt%, preferably about 0.01 to about 2 wt% and more preferably about 0.01 to about 1 wt% of molybdenum(VI) compound based on the oil.
  • Suitable lubricating base oils are mineral oils, petroleum oils, synthetic lubricating oils, and natural lubricating oils of animal or vegetable origin. Concentrates of the additive in appropriate base oils containing about 10 to about 90 weight percent of the additive based on the oil are convenient for producing finished lubricants by dilution with additional base oil.
  • a variety of other additives can be used beneficially with the additives of this invention, including antioxidants, dispersants, corrosion inhibitors, wear inhibitors, friction modifiers, detergents, antibacterial agents, antifoam agents, etc.
  • the gasoline soluble molybdenum compounds are tested for ORI suppression and elevated steady state octane requirement reduction using the CRC E-15 technique with primary reference fuels and full boiling range reference fuels on an engine dynomometer.
  • a GM 3.7 liter (231 cubic inch) V-6, and a Ford 2.3 liter (140 cubic inch) 4-cylinder in-line engine were connected to a load dynomometer.
  • the fuel line is connected via a valve to a test fuel containing various concentrations of molybdenum compound and other containers containing standard fuel having known octane numbers.
  • the conditions of the test are as follows: the temperature of the coolant and oil is maintained at 93°C (200°F) ⁇ 6°C (10°F), the temperature of the inlet air was 40°C-49°C (110°F-120°F), and the temperature of the transmission was maintained at 82°C (180°F) ⁇ 6°C (10°F).
  • the air/fuel ratio was held at about stoichiometric, ignition timing and exhaust gas recirculation was maintained at the stock value.
  • the engine was operated on fuel with and without gasoline soluble molybdenum compound for up to 30,000 equivalent miles. At intervals of 4,000 equivalent miles the standard test fuels were burned in the engine to determine the octane requirement of the engine. After the octane requirement was determined the engines were returned to the test fuel.
  • distillation trap and condenser assembly Into a 500 ml, three-neck flask equipped with a mechanical stirrer, thermometer, sparge assembly, side arm adapter and dropping funnel, distillation trap and condenser assembly was charged 104.8 grams (0.2 mole) of the above reaction product, 28.8 grams (0.2 mole) molybdenum trioxide and 100 milliliters of xylene. The mixture was stirred and heated to 149°C. Water was removed azeotropically with a nitrogen stream. After 30 minutes at 149°C, 3.6 milliliters of water were removed. The product was filtered through celite and isolated by stripping to 149°C with nitrogen.
  • the dark brown product which solidified on cooling, contained 11.8 wt% molybdenum and was identified as dioxo- N , N ⁇ -(2-oxo-4-nonylbenzyl)ethylenediamino­molybdenum(VI).
  • the mixture was stirred and heated at reflux for 4.25 hours. Water of reaction was removed by azeotropic distillation, and the mixture was centrifuged. The product was filtered and stripped of heptane by heating to 138°C with a nitrogen stream. The product contained 2.2 wt% molybdenum, 1.31 wt% nitrogen, and had a 40°C viscosity of 2516 SSU.

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Abstract

An unleaded gasoline in combination with a minor amount of a gasoline soluble molybdenum(VI) compound is effective in reducing elevated steady state octane requirement and suppressing octane requirement increase in spark ignition internal combustion engines.

Description

    Background of the Invention 1. Field of the Invention.
  • This invention relates to improved unleaded gaso­line compositions. More particularly, the invention relates to the incorporation of molybdenum(VI) compounds into an unleaded gasoline for the purpose of reducing elevated steady state octane requirement and suppressing octane requirement increase in spark ignition internal combustion engines.
  • 2. Description of the Prior Art.
  • A great number of gasoline additives, including antiknock agents, deposit reducing agents, demulsifiers, etc., have been developed in recent years. A commer­cially important antiknock agent, tetraalkyl lead, has, until recently, been universally used to prevent engine knock by increasing the octane number of gaso­line. However, with increased sensitivity to lead in the environment and with the use of catalytic conver­ters that can be poisoned by lead, broad restrictions have been placed on the use of lead in gasoline. In the absence of lead, greater amounts of expensive, high octane blending stock must be used to produce gasoline having sufficient octane for current produc­tion automobiles.
  • Along with the increased cost of production of unleaded gasoline, a particularly harmful problem has arisen. Engines operating on unleaded gasoline commonly experience increasing incidence and severity of knock as they age. A new or "clean" engine can operate efficiently and without knock using a gasoline having a research octane number of about 85. The same engine with about 8,000-12,000 accumulated miles can often require a gasoline having an octane number about 95-­100 or higher. This increase in the octane number required to prevent knock is called octane requirement increase (ORI).
  • ORI is believed to be one result of thermally insulating combustion chamber deposits formed from gasoline contaminants and from the incomplete combus­tion of gasoline and lubricating oil. Initially the rate of deposit formation is substantially greater than the rate of disintegration, and the deposits rapidly build. As the deposits thicken, the rate of disintegration approaches and eventually equals the rate of formation. At this point, the deposits reach a steady state thickness. Knock in the engine appears to increase in incidence and severity as the deposit builds and reaches a constant or steady state elevated rate of incidence and severity corresponding to the steady state thickness of the deposit. At this point the engine commonly has an elevated steady state octane requirement which can be 2 to 15 research octane numbers greater than the octane requirement when new.
  • While we do not wish to be limited to a theory of ORI, we believe that the combustion chamber deposits have the substantial ability to prevent transfer of thermal energy from the combustion chamber into engine coolant, causing accumulation of thermal energy in the deposits and in the combustion chamber. When a spark ignites the air/fuel mixture in the combustion chamber, a flame front is initiated and combustion rapidly and smoothly progresses from the spark plug to the "end-gas region" opposite to the spark plug. The high pressure flame front rapidly compresses the unburned air/fuel mixture which is at a relatively lower pressure in the end-gas region as the front progresses through the chamber. Commonly, the combustion progresses through the combustion chamber, and knock is not heard. However, if the temperature of the combustion chamber and the air/fuel mixture has been substantially increased by the insulating properties of the deposits, the rapid compression of the air/fuel mixture in the end-gas region causes an immediate autodetonation which is different than normal progressive combustion. This autodetonation causes the "knocking" or "pinging" sound, can reduce operating efficiency and can cause engine damage. See J. D. Benson, "Some Factors Which Affect Octane Requirement Increase," SAE Paper 750933, Detroit, Michigan, October 1975, for a detailed treatment of ORI.
  • ORI can readily be remedied with leaded gasoline by increasing the lead concentration. In unleaded fuels, a greater amount of high octane blending stock must be used to increase the octane. However, high octane blending stock commonly contains aromatic con­stituents that are more likely to leave thermally insulating deposits and increase ORI.
  • With the suppression of ORI, more gasoline with a lower octane number could be produced per barrel of crude oil at lower cost. Since the production of high octane gasoline consumes more energy than the production of lower octane gasoline, refining operations would become more energy efficient. Further, in the absence of ORI, engine manufacturers could build more fuel efficient engines by increasing compression and adjusting spark timing. Such engines would perform satisfactorily with a fuel having the same or lower octane as is currently available.
  • In this application, octane requirement increase shall mean the gradual increase in octane requirement observed as an engine ages. Elevated steady state octane requirement shall mean the octane requirement of an engine with combustion chamber deposits that have reached a steady state both in thickness and in resistance to thermal energy flow.
  • The incorporation of certain specific molybdenum compounds into gasoline has been suggested for the purpose of providing a composition having improved lubricating and antiwear properties. U.S. Patent Nos. 4,164,473; 4,176,073; and 4,176,074 disclose the use of molybdenum complexes of hydroxy amines, molyb­denum complexes of lactone oxazoline dispersants, and molybdenum complexes of oxazoline dispersants respec­tively for this purpose. Similarly, U.S. Patent Nos. 4,192,757 and 4,201,683 disclose, for this purpose, the use of molybdenum complexes which are obtained by reaction of a hydrocarbyl substituted thio-bis-phenol with a molybdenum compound in the presence of an amine in an alkyl substituted phenol or alkanol solvent, respectively. In addition, U.S. Patent No. 3,994,697 teaches that a solid pellet comprising various metals in combination with molybdenum disulfide can be placed in the fuel reservoir of an internal combustion engine where it slowly disintegrates to produce extremely minute particles which are dispersed in the fuel and are delivered to the fuel-contacting parts of the engine to deposit a lubricant film thereon.
  • U.S. Patent Nos. 3,615,293 and 3,755,195 disclose the incorporation of various organic molybdenum com­pounds into a gasoline fuel which contains an organo­manganese antiknock agent. These patents teach that the molybdenum compounds are effective in reducing spark plug fouling by gasoline fuels which contain organomanganese antiknock agents. It is further disclosed that suitable organic molybdenum compounds include molybdenum salts and chelates. However, these references fail to suggest the incorporation of a molybdenum compound into gasoline for any purpose in the absence of an organomanganese antiknock agent.
  • U.S. Patent No. 3,317,571 discloses the prepara­tion of organomolybdenum compounds wherein one or more molecules containing an amide or thioamide linkage are bonded to the molybdenum atom through a sulfur or oxygen linkage and which is stabilized by additional covalent bonding to a plurality of carbonyl groups. This patent discloses that such compounds can be used in gasoline, either alone or in combination with lead alkyls, as antiknock agents. It fails, however, to either teach or suggest the use of a molybdenum(VI) compound for any purpose.
  • U.S. Patent No. 3,272,606 discloses that small amounts of a covalent molybdenum polycarbonyl compound can be used in gasoline in combination with an organo­lead antiknock agent to enhance the antiknock properties of the organolead antiknock agent. However, this reference fails to suggest the incorporation of a molybdenum compound into gasoline for any purpose in the absence of an organolead antiknock agent.
  • U.S. Patent No. 2,086,775 is directed to the incorporation of various organometallic compounds into a liquid fuel for an internal combustion engine. Suitable organometallic compounds are those of cobalt, nickel, manganese, iron, copper, uranium, molybdenum, vanadium, zirconium, beryllium, platinum, palladium, thorium, chromium, aluminum, and the rare earth metals. In addition, the liquid fuel may also contain an organolead antiknock agent. It is disclosed that use in an internal combustion engine of a fuel containing small amounts of these organometallic compounds results in the formation of a catalytic deposit within the combustion chambers of the engine which is effective for the elimination of knock and the improvement of combustion within the engine. However, this patent offers no guidance for selecting a molybdenum(VI) compound for use in a gasoline composition which is substantially free of other metals for the purpose of suppressing octane requirement increase and reducing elevated steady state octane requirement in spark ignition internal combustion engines.
  • U.S. Patent No. 3,155,620 is directed to the use of cycloheptatriene transition metal coordination compounds of the Group VIB metals as additives for liquid hydrocarbon compositions. This patent teaches that such additives can be used to increase the octane of liquid fuels and to provide improved lubricating properties when incorporated into lubricating oil compositions. It is further disclosed that these coordination compounds can be used in combination with antiknock agents such as organolead compounds. However, this patent fails to either teach or suggest the use of a molybdenum(VI) compound for any purpose.
  • U.S. Patent No. 3,440,028 is directed to the incorporation of a metal halide hydrocarbyl orthophos­phate additive into leaded gasoline compositions for the purpose of suppressing the tendency of the lead to increase undesirable surface ignition within the combustion chambers of an engine. The metal of the additive can be selected from the group consisting of manganese and metals of Groups IB, IIA, IIB, IVA, VIB and VIII of the Periodic Table. Similarly, U.S. Patent No. 3,240,576 discloses that the addition to leaded gasoline of a gasoline soluble organomolybdenum com­pound will provide a substantial reduction of surface ignition in the combustion chambers of a spark ignition internal combustion engine. These patents do not, however, suggest the addition of a molybdenum compound to unleaded gasoline for any purpose.
  • U.S. Patent No. 3,401,184 is directed to a method for the preparation of metal organo orthophosphates wherein the metal can be selected from Groups II, IV, VI and VIII of the Periodic Table. It is disclosed that these compounds have utility as gasoline additives and that when so used they impart rust inhibition, surface ignition suppression, carburetor detergency, carburetor icing alleviation and reduction in octane requirement increase to the gasoline composition. In addition, U.S. Patent No. 3,282,838 discloses the use of amine salts of chromic or molybdic acid as corrosion inhibitors in petroleum hydrocarbons such as gasoline. These amine salts contain either a chromic or molybdic ion of +6 valence and are used at a concentration level between about 0.005 and 5 weight percent.
  • Finally, U.S. Patent No. 3,003,859 discloses the incorporation into a liquid hydrocarbon, such as gaso­line, of about 0.005 to about 5 percent by weight of a metal-organic material which is obtained by heating a normally-solid metallic chelate compound formed from a beta-keto ester to a temperature above its melting point. It is further disclosed that these metal chelates can be formed from metallic elements of the Periodic Table comprising the Groups IA, IB, IIA, IIB, IIIA, IIIB, IVA, IVB, VA, VB, VIB, VIIB and VIII including the lanthanide and actinide series of rare earth elements. This patent, however, fails to offer any guidance for selecting a molybdenum(VI) compound for the purpose of suppressing octane require­ment increase and reducing elevated steady state octane requirement in spark ignition internal combustion engines.
  • Summary of the Invention
  • The present invention is directed to the discovery that the incorporation of small amounts of a gasoline soluble molybdenum(VI) compound into unleaded gasoline affords a fuel composition which is effective in reducing elevated steady state octane requirement and suppressing octane requirement increase in spark igni­tion internal combustion engines.
  • One embodiment of the invention is a gasoline fuel composition comprising a major proportion of a liquid hydrocarbon fuel of gasoline boiling range in combination with a molybdenum(VI) compound which is soluble in said hydrocarbon fuel, wherein the amount of said molybdenum(VI) compound is from about 0.1 to about 20.0 parts per one million parts of hydrocarbon fuel, said fuel composition is substantially free of metals other than molybdenum, and said molybdenum(VI) compound is selected from the group consisting of molybdenum(VI) sulfonates, molybdenum(VI) diamine complexes, amine salts of molybdic acid and isopoly­molybdic acid, and molybdenum(VI) compounds which are free of nitrogen, sulfur and phosphorus.
  • Another embodiment of the invention is a gasoline fuel composition comprising a major proportion of a liquid hydrocarbon fuel of gasoline boiling range in combination with a molybdenum(VI) compound which is soluble in said liquid hydrocarbon fuel, wherein the amount of said molybdenum(VI) compound is effective to suppress octane requirement increase in a spark ignition internal combustion engine, said fuel composi­tion is substantially free of metals other than molyb­denum, and said molybdenum(VI) compound is selected from the group consisting of molybdenum(VI) sulfonates, molybdenum(VI) diamine complexes, amine salts of isopoly molybdic acid, and molybdenum(VI) compounds which are free of nitrogen, sulfur and phosphorus.
  • Another embodiment of the invention is a gasoline fuel composition comprising a major proportion of a liquid hydrocarbon fuel of gasoline boiling range in combination with a molybdenum(VI) compound which is soluble in said liquid hydrocarbon fuel, wherein the amount of said molybdenum(VI) compound is effective to reduce elevated steady state octane requirement in a spark ignition internal combustion engine, said fuel composition is substantially free of metals other than molybdenum, and said molybdenum(VI) compound is selected from the group consisting of molybdenum(VI) sulfonates, molybdenum(VI) diamine complexes, amine salts of isopoly molybdic acid, and molybdenum(VI) compounds which are free of nitrogen, sulfur and phosphorus.
  • A further embodiment of the invention is a method for reducing elevated steady state octane requirement in a spark ignition internal combustion engine and maintaining the resulting reduced steady state octane requirement which comprises operating said engine on a first gasoline fuel composition until a reduced steady state octane requirement is achieved and main­taining said reduced steady state octane requirement by operating the engine on a second gasoline fuel composition, wherein said first fuel comprises a major proportion of a liquid hydrocarbon fuel of gasoline boiling range in combination with an amount of a soluble molybdenum(VI) compound which is sufficient to provide from about 10 to about 1000 parts of molyb­denum per million parts of liquid hydrocarbon fuel, wherein said second fuel comprises a major proportion of a liquid hydrocarbon fuel of gasoline boiling range in combination with an amount of a soluble molyb­denum(VI) compound which is sufficient to provide from about 0.01 to about 10 parts of molybdenum per million parts of liquid hydrocarbon fuel, and wherein both of said first and second fuels are substantially free of lead.
  • A further embodiment of the invention is a method for reducing elevated steady state octane requirement and/or suppressing octane requirement increase in a spark ignition internal combustion engine which comprises operating said engine with a gasoline fuel composition comprising a major proportion of a liquid hydrocarbon fuel of gasoline boiling range in combina­tion with a molybdenum(VI) compound which is soluble in said liquid hydrocarbon fuel, wherein the amount of said molybdenum (VI) compound is effective to reduce elevated steady state octane requirement and/or sup­press octane requirement increase in said engine, said fuel composition is substantially free of metals other than molybdenum, and said molybdenum (VI) compound is selected from the group consisting of molybdenum (VI) sulfonates, molybdenum (VI) diamine complexes, amine salts of molybdic acid and isopoly molybdic acid, and molybdenum (VI) compounds which are free of nitrogen, sulfur and phosphorus.
  • A still further embodiment of the invention is a method for reducing elevated steady state octane requirement in a spark ignition internal combustion engine having an increased octane requirement of about 2 to about 7 units after operation with gasoline substantially free of lead and molybdenum which com- prises operating said engine with a gasoline fuel composition comprising a major proportion of a liquid hydrocarbon fuel of gasoline boiling range in combina- tion with a molybdenum (VI) compound which is soluble in said hydrocarbon fuel, wherein the amount of said molybdenum (VI) compound is sufficient to provide from about 10 to about 1000 parts of molybdenum per million parts of said hydrocarbon fuel, and the amount of said gasoline fuel composition is effective to reduce said elevated steady state octane requirement by at least about 20%.
  • The general object of this invention is to sup-­press ORI and reduce elevated steady state octane requirement arising in internal combustion engines using unleaded fuels. Another object is to modify the thermal conductivity of combustion chamber deposits to increase heat conduction and thereby reducing elevated steady state octane requirement and suppressing ORI. Still another object of the invention is to promote the formation of thermally conductive deposits in internal combustion engines. A further object of the invention is to provide low octane gasoline that can be used in an engine without harmful knock arising as the engine ages. A still further object of the invention is to increase the efficiency of gasoline production by producing more low octane gasoline from crude oil.
  • Detailed Description of the Invention
  • We have discovered that the octane requirement increase and the elevated steady state octane require­ment caused by combustion chamber deposits in internal combustion engines can be prevented or reduced by operation of an internal combustion engine wherein the combustion processes in the combustion chamber are performed in the presence of a hexavalent molyb­denum, molybdenum(VI) or molybdenum +6 compound. The hexavalent molybdenum compound can be provided to the combustion chamber by a gasoline substantially free of lead compounds containing a gasoline soluble hexa­valent molybdenum compound, or by a lubricating oil containing the molybdenum compound which is transported into the combustion chamber during the operation of the engine. We have further discovered certain pre­ferred hydrocarbon soluble compounds containing molyb­denum in the +6 oxidation state that are effective in preventing octane requirement increase and are effective in reducing elevated steady state octane requirement.
  • The generic use of molybdenum compounds of any oxidation state to prevent octane requirement increase and reduce elevated steady state octane requirement has been investigated by us previously. However, now we have found that only molybdenum(VI) compounds serve to efficiently afford these results. Apparently, only molybdenum(VI) compounds efficiently alter the thermal energy transfer characteristics of combustion chamber deposits so that heat can be rapidly conducted from combustion chamber to engine coolant. Since the modified deposits no longer impede efficient removal of heat from the combustion chamber, the gasoline is ignited solely by the spark and the fuel is burned uniformly in the combustion chamber, efficiently transmitting combustion energy to the road in the absence of knock, ping, loss in efficiency or mechanical damage.
  • Although the subject invention is not to be so limited, it is believed that a greater thermal con­ductivity per unit mass of combustion chamber deposit results from higher levels of organic oxygen and that such highly oxidized deposits are generated efficiently in the presence of molybdenum only when the molybdenum is in the +6 oxidation state. In principle, molybdenum of lower oxidation state could be oxidized to the +6 oxidation state within an engine during the combustion of fuel. However, the conditions under which gasoline is combusted in a spark ignition internal combustion engine appear to be unsuitable to render such a process of significance. Among other possible factors, it is believed that the fuel combustion cycles are too short to effect such a modification of molybdenum oxidation state.
  • Briefly, the improved gasoline compositions of this invention can be prepared by combining with a major portion of gasoline substantially free of lead compounds an effective octane requirement increase suppressing or an effective steady state octane requirement reducing amount of a gasoline soluble compound containing molybdenum(VI), hexavalent molyb­denum, or molybdenum +6. The improved lubricants of the invention can be prepared by combining with a lubricant an effective amount of a hydrocarbon soluble molybdenum(VI) compound.
  • One aspect of the invention is an unleaded gaso-­line, used in "clean," new engines, containing a low concentration of a hydrocarbon soluble molybdenum (VI) compound comprising a major portion of gasoline and about 0.1 to about 20 parts of the molybdenum (VI) compound per one million parts of gasoline. Alterna-­tively, such a molybdenum (VI) compound can be used in an amount which is sufficient to provide from about 0.01 to about 10 parts of molybdenum, calculated as the metal, per million parts of gasoline.
  • Another aspect of the invention is a gasoline, for use in "dirty" engines that have reached an elevated steady state octane requirement caused by deposits in the combustion chamber, to substantially reduce the elevated steady state octane requirement. This composition, which modifies the existing deposits and reduces the elevated steady state octane require-­ment, comprises a major portion of gasoline and about 20 to about 10,000 parts of a hydrocarbon soluble molybdenum (VI) compound per one million parts of gasoline. Alternatively, such a molybdenum (VI) com-­pound can be used in an amount which is sufficient to provide from about 10 to about 1000 parts of molybdenum, calculated as the metal, per million parts of gasoline.
  • A further aspect of the invention is a concentrate of a hydrocarbon soluble molybdenum (VI) compound con-­taining about 0.1 to about 50 wt% of the compound in a suitable diluent which can be dissolved in proper proportion in gasoline or lubricating oil to provide about 0.1 to about 10,000 parts of molybdenum (VI) compound per one million parts of gasoline or about 0.001 to about 5 wt% of molybdenbum (VI) compound in a lubricating oil.
  • A still further aspect of the invention is a lubricating oil containing a hydrocarbon soluble molyb­denum compound which when used to lubricate an engine provides to the combustion chamber a substantial amount of molybdenum(VI), by oxidation of a molybdenum com­pound or by other means, that can suppress ORI or reduce elevated steady state octane requirement. Commonly, lubricating oils contain about 0.001 to about 5 wt%; preferably about 0.01 to about 2 wt%; and most preferably, to reduce molybdenum consumption and provide maximum benefit, about 0.01 to about 1 wt% of molybdenum(VI) compound.
  • Significant amounts of lead and manganese com­pounds have been widely used in gasoline as antiknock agents. Lead compounds, particularly tetraalkyl lead compounds, have been most extensively used, whereas manganese compounds have been primarily used to enhance the antiknock properties of lead compounds. However, the molybdenum(VI) containing gasoline compositions of this invention are preferably substantially free of lead, more preferably substantially free of both lead and manganese, and most preferably substantially free of metals other than molybdenum.
  • Any hydrocarbon soluble molybdenum(VI) compound which is stable in hydrocarbon or petroleum storage or distribution facilities can be used in gasoline in accordance with this invention. Preferably, the molybdenum(VI) or compound is selected from the group consisting of molybdenum(VI) sulfonates, molybdenum(VI) diamine complexes, amine salts of molybdic acid and isopoly molybdic acid, and molybdenum(VI) compounds which are free of nitrogen, sulfur and phosphorus. More preferably, the molybdenum(VI) compound is selected from the group consisting of molybdenum(VI) sulfonates, molybdenum(VI) diamine complexes, amine salts of isopoly molybdic acid, molybdenum(VI) carboxylates, molybdenum(VI) salts of naphthenic acids, molybdenum(VI) phenates, molybdenum(VI) alkoxides, molybdenum(VI) aryloxides, and molybdenum(VI) beta-diketone complexes.
  • Although phosphorus containing compounds of molybdenum(VI) can be used in the practice of this invention, they are ordinarily not preferred. This is a consequence of the fact that phosphorus is considered to be harmful to the catalytic converters which are currently employed to control the emission of hydrocarbons, carbon monoxide and nitrogen oxides from automotive engines.
  • Molybdenum compounds useful to suppress ORI or reduce elevated steady state octane requirement include a broad variety of molybdenum(VI) compositions.
  • A useful class of molybdenum(VI) compositions can be formed by the reaction of molybdenum in a variety of forms with a ligand. Examples of these ligands are acetylacetone, N-nitrosophenylhydroxylamine, dimethylglyoxime, ethylenediamine, ethylenediamine­tetraacetic acid, nitrilotriacetic acid, 8-hydroxy­quinoline, benzoylacetone, 2,4-pentanediene, beta-­diketones, oxygen, halogens, Mannich products, phosphates, phosphine oxides, alkanol amines, sulfoxides formamides and other similar well known chelating agents.
  • Another useful class of hydrocarbon soluble molybdenum compositions includes molybdenum(VI) beta-­diketonates wherein the beta-diketone can be represented by the formula:
    Figure imgb0001
    At least one proton on the carbon atom between the carbonyl groups is necessary for the formation of the molybdenum complex. The removal of this proton generates a beta-diketone anion which can chelate the metal ion present. R¹ and R² are hydrocarbyl groups of 1 to 50 carbon atoms and include primary, secondary and tertiary alkyl, alkenyl and aromatic groups. Preferred alkyl groups are methyl, ethyl, isopropyl, t-butyl, sec-amyl, 2-ethylhexyl, eicosyl, pentacontyl, having both normal chains and branched chains. R³ can be hydrogen or a hydrocarbyl group of 1 to 50 carbon atoms. Preferably, R³ is hydrogen or an alkyl group, for example methyl, ethyl, isopropyl, t-butyl, amyl,n-hexyl, pentacontyl, etc., having both normal and branched chain.Beta-diketones are well known in the art, some are available commercially, and all are readily prepared by methods well known in the art.
  • The commonly used compounds are prepared from beta-diketones wherein R¹ and R² represent alkyl groups of 1 to 20 carbon atoms and R³ represents hydrogen. More specifically, the preferred beta-diketones are 2,4-pentanedione, 3-methyl-2,4-pentanedione, 3-isopropyl-­2,4-pentanedione, 2,4-hexanedione, 2-methyl-3,5-­hexanedione, 4-methyl-3,5-heptanedione, 3,5-heptanedione, 2,6-dimethyl-3,5-heptanedione, 2-methyl-4,6-heptanedione, 2-methyl-4,6-octanedione, 2,8-dimethyl-4,6-nonanedione, and 2,2,6,6-tetramethyl-3,5-heptanedione. Other beta-­diketone complexes are discussed by Morgan and Castell, J. Chem. Soc., 3252 (1928).
  • Another useful class of hydrocarbon soluble molybdenum(VI) complexes that can be used in the practice of this invention is composed of molybdenum(VI) diamine complexes wherein the diamine ligand is represented by:

        R⁴R⁵N-(CR⁴R⁵)n-NR⁴R⁵

    wherein n is an integer from 1 to 20, preferably for reasons of stability of the molybdenum-amine product, n is 2 to 4. The R⁴ and R⁵ substituents can be independently hydrogen or alkyl of 1 to 20 carbon atoms and the amino groups can be independently primary, secondary or tertiary groups. Representative diamines include ethylenediamine, 1,2-propylenediamine, 1,3-­ propylenediamine, 2-methyl-1,3-diaminopropane, 2,2-­dimethyl-1,3-diaminopropane, ortho-phenylenediamine and the corresponding 1 to 20 carbon alkyl-substituted diamines.
  • Other useful hydrocarbon soluble molybdenum(VI) compounds include molybdenum-polyamine Mannich complexes, molybdenum-polyamine substituted dicarboxylic acid complexes, disclosed in U.S. Serial No. 190,590, filed September 25, 1980, which is expressly incorporated by reference herein.
  • Another useful class of molybdenum(VI) compositions includes the neutralization products of molybdic acid including iso and heteropoly molybdic acid with an oil soluble base and the neutralization of an acid with a molybdenum base.
  • Gasoline soluble amine salts of the formula:
        [R⁶R⁷R⁸NH]₂MoO₄
    can be used in the practice of this invention wherein R6 is a hydrocarbyl radical, and R⁷ and R⁸ are independently selected from the group consisting of hydrogen and hydrocarbyl. Typical hydrocarbyl radicals include, for instance: alkyl, alkenyl, aryl, alkaryl, arylalkyl, or alicyclic radicals. Examples of suitable hydrocarbyl radicals are : methyl, ethyl, propyl, butyl, isohexyl, 2-ethylhexyl, neodecyl, dodecyl, octadecyl, eicosyl, nonacosyl, phenyl, naphthyl, benzyl, cresyl, ethylphenyl, phenylhexyl, cyclohexyl, cyclo­propyl, cyclopentyl, butenyl, octenyl, linoleyl, etc.
  • Another useful class is composed of hydrocarbon soluble molybdenum(VI) dialkyl phosphates, phosphoro­thioates and phosphorodithioates which are derived from a phosphorus containing moiety of the formula:
    Figure imgb0002
    wherein each X can be independently selected from oxygen or sulfur and each R⁹ is independently selected from hydrocarbon alkyl and aryl groups having from one to about 30 carbon atoms. Examples of these molybdenum(VI) compositions are:
    molybdenum-dimethylphosphorothioate
    molybdenum-dioctylphosphorothioate
    molybdenum-diphenylphosphate
    molybdenum-dicresylphosphate
    molybdenum-didecylphosphorodithioate
    molybdenum-diamylphosphorotetrathioate
    molybdenum-di-tert-butylphosphorotrithioate
    molybdenum-dixylylphosphorothioate
    molybdenum-di-4-ethylphenylphosphorotrithioate
    molybdenum-dioctadecylphosphorotetrathioate
    molybdenum-cresylphenylphosphate
    molybdenum-dinaphthylphosphorothioate
    molybdenum-diisopropylphosphorothioate
    molybdenum-dibenzylphosphate
    molybdenum-dicresylphosphorodithioate
    molybdenum-di-4-dodecylphenylphosphorodithioate
    molybdenum-dibenzylphosphorodithioate
    molybdenum-dilaurylphosphorodithioate
    molybdenum-di-2-ethylhexylphosphorodithioate
    molybdenum-dicyclohexylphosphorodithioate
    molybdenum-diisoamylphosphorodithioate
    molybdenum-dioctadecylphosphorodithioate
    molybdenum-diundecylphosphorodithioate
    molybdenum-diheptylphosphorodithioate
    molybdenum-di-2,6-tert-butylphenylphosphorodithioate
    molybdenum-diethylphosphorodithioate
    molybdenum-ditetradecylphosphorodithioate
    molybdenum-diacetylphosphorodithioate
    molybdenum-di-2,4-didodecylphenylphosphorodithioate
    molybdenum-dihexylphosphorodithioate
    and the like. Other compounds are taught by Revukas in U.S. Patent Nos. 3,440,028 and 3,401,184 which are expressly incorporated by reference herein. However, phosphorus is currently considered harmful to catalytic converters. Consequently, phosphorus containing com­pounds are not preferred for use in the practice of this invention.
  • Still another class of hydrocarbon soluble molybdenum(VI) compounds which can be used in accordance with this invention comprises molybdenum(VI) car­boxylates such as those disclosed by Cavitt in U.S. Patent No. 3,595,891 and Hnizda in U.S. Patent No. 3,755,195 which are expressly incorporated by reference herein.
  • Examples of suitable molybdenum(VI) carboxylates of this type are molybdenum pentanoate, molybdenum octanoate, molybdenum oleate, molybdenum linoleate, molybdenum adipate, molybdenum 2-ethylhexanoate, molybdenum benzoate, molybdenum tetradecanoate, molyb­denum orthophthalate, molybdenum 4-dodecylbenzoate, molybdenum stearate, molybdenum laurate and the like. Molybdenum(VI) salts of mixtures of fatty acids obtained from natural products such as olive oil, tall oil, cottonseed oil, tallow, coconut oil and the like are also useful. Other molybdenum(VI) compounds of this type are the salts of alicyclic carboxylic acids. Specific examples of useful molybdenum(VI) salts of alicyclic carboxylic acids are molybdenum cyclopentanecarboxylate, molybdenum cyclopentylacetate, molybdenum 3-methylcyclopentylacetate, molybdenum camphoate, molybdenum cyclohexanecarboxylate, molyb­denum 3-dodecylcyclohexanecarboxylate, molybdenum 2,6-dicyclohexylcyclohexanecarboxylate, molybdenum 2-cyclohexyl-4,6-dipentyl-4-methylcyclohexanecarboxylate, molybdenum 4-methylcyclohexanecarboxylate, molybdenum 2,2,6-trimethylcyclohexanecarboxylate and the like.
  • Another class of hydrocarbon soluble molybdenum(VI) compositions which is useful in the practice of this invention are salts of the so-called naphthenic acids. The term "naphthenic acids" is applied to a mixture of carboxylic acids obtained from the alkali washes of petroleum. These acids are complex mixtures of normal and branched aliphatic acids, alkyl derivatives of cyclopentane- and cyclohexane-carboxylic acids and cyclopentyl and cyclohexyl derivates of aliphatic acids. The alicyclic carboxylic acids appear to be the major constituents of these mixtures. The composi­tion of these naphthenic acids will vary depending on factors such as the source of petroleum, the refining procedure, etc. A more detailed discussion of these naphthenic acids is presented in "Chemical Technology of Petroleum," William A. Gruse and Donald R. Stevens, 3rd edition, pp. 65-67, 1960, McGraw-Hill Publishing Company, which is incorporated by reference.
  • Molybdenum(VI) sulfonates wherein the sulfonate moiety has the general formula:
        ArSO
    Figure imgb0003

    can also be used in the practice of this invention. Sulfonic acid compounds useful to prepare molybdenum(VI) sulfonates can have the following general formula:
        XSO₃-(Ar)n-A m
    wherein A is hydrogen, an alkyl, or other hydrocarbyl group with hydroxy-, chloro-, or bromo-substituents; Ar is an aryl unit including benzene, naphthalene, etc.; m is an integer of 1 to 5; n is an integer of 0 to 5; and X is a halogen or hydrogen. A can be any substantially hydrocarbyl or substituted hydrocarbyl group which results in a hydrocarbon benzene sulfonic acid. A can be a hydrogen or a substantially aliphatic group with about 1 to 15 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, nonyl, decyl, dodecyl, pentadecyl and the like, with a molecular weight of about 120 and greater; an intermediate molecular weight alkyl group such as polyisobutylene or polypropylene polymers with 15 to 1,000 carbon atoms with a molecular weight of about 200 to 14,000; a high molecular weight hydrocarbyl such as polyolefin having a number average molecular weight in excess of 14,000; and others. A can be substituted with groups such as chlorine, bromine, or hydroxy groups. Also, Ar can have more than one substituent, for example, alkyl, hydroxyalkyl, or haloalkyl.
  • Other suitable oil soluble benzenesulfonic acids are the oil soluble, so-called petroleum sulfonic acids which are also commonly referred to as mahogany acids, having a molecular weight from about 350 to 750, aryl sulfonic acids, and alkaryl sulfonic acids. Examples of other suitable sulfonic acids are diparaffin wax-substituted phenolsulfonic acid, cetylchlorobenzene­sulfonic acid, cetylphenoldisulfidesulfonic acid, cetylphenolmonosulfidesulfonic acid, etc. Other suitable oil-soluble sulfonic acids are well described in the art such as U.S. Patent Nos. 2,616,604; 2,626,207; 2,767,209; and others. The inexpensive, low molecular weight polypropylbenzenesulfonic acids having a molecular weight of about 200 to 1,200 are preferred.
  • Another class of useful compounds is comprised of molybdenum(VI) phenates which are the reaction product of a molybdenum compound and a phenol compound. Examples of useful phenol compounds include:
    4-methylphenol,
    4-octadecylphenol,
    4-oleylphenol,
    4-(2-ethyl-n-hexyl)phenol,
    2,6-dimethylphenol,
    2,4,6-trimethylphenol,
    o-chlorophenol,
    2-dodecylphenol,
    2,4-didodecylphenol,
    p-nonylphenol,
    2-tert-butylphenol
    , 4-dodecylphenol,
    4-polyisobutylene substituted phenol,
    and the like.
  • An especially useful type of a molybdenum(VI) phenate is that derived from a commercial mixture of alkylated phenols. Commercial alkylation of phenols generally is accomplished by treating the phenol with an olefin, or polyolefin or mixtures thereof in the presence of an alkylating agent. This commercial alkylation ordinarily produces a mixture of various alkyl phenols. For example, if a phenol is alkylated with a C₉ olefin, the product will contain monononyl­phenols, dinonylphenols, and trinonylphenols. Likewise, if a mixture of C₉, C₁₀, and C₁₈ olefins is used in the alkylation, a mixture of various C₉, C₁₀, and C₁₈ alkylated phenols is obtained.
  • Still another class of hydrocarbon soluble molyb­denum(VI) compounds includes alkoxides and aryloxides that can be prepared by reacting a molybdenum halide compound with an alcohol or a phenol, for example:
        MoO₂Cl₂ + 2ROH = MoO₂(OR)₂ + 2HCl
  • Preferred hydrocarbon soluble molybdenum(VI) compounds, for reasons of solubility in gasoline and lubricating oil and the substantial reduction of octane requirement increase and equilibrium octane requirement, include cis-dioxobis(dipivaloyl­methanato)molybdenum(VI), MoO₂(THD)₂ and trans-­dioxobis(dipivalolylmethanato)molybdenum(VI), molybdenum(VI) octoate and naphthanate, methylenebis(2-­oxo-4-dodecylphenol)molybdenum(VI), dioxo-N,Nʹ-(2-­oxo-4-nonylbenzyl)ethylenediaminemolybdenum(VI), molybdenum(VI) sulfonate, and molybdenum(VI) polyamine-­Mannich complex comprising the reaction product of a molybdenum compound and a Mannich reactant product of an alkylphenol, formaldehyde, or a formaldehyde-yielding compound and a polyamine, and the reaction product of a molybdenum compound with the material formed by reacting an olefin with phosphorus pentasulfide.
  • The foregoing compounds are intended to be exemplary of hydrocarbon soluble molybdenum(VI) com­pounds known and preferred at this time, and should not be used to unduly limit the scope of the invention.
  • In somewhat greater detail, the improved gasolines and lubricants of this invention having the ability to prevent substantial octane requirement increase and to reduce high equilibrium octane requirement are produced by combining a gasoline or a lubricating oil with an amount of a hydrocarbon soluble hexavalent molybdenum compound which is effective to reduce ele­vated steady state octane requirement and/or suppress octane requirement increase.
  • Varying threshold concentrations exist for each of many molybdenum(VI) compounds for reduction of the octane requirement increase. The threshold for each compound lies between about 0.01 and 3.0 parts of molybdenum per one million parts of gasoline. The threshold concentration varies due to the effect on the molybdenum of the radicals or groups attached. In new engines, the concentration of the molybdenum can range from 0.01 to about 10 parts of molybdenum per million parts of gasoline to prevent substantial increase in octane requirement. In "dirty" engines, i.e., engines that have been operated on unleaded gasoline not containing molybdenum compounds, which have reached a high steady state octane requirement, a gasoline containing about 10 to about 1000 parts of molybdenum per million parts of gasoline can be used until the steady state octane requirement has been reduced to near the "clean" octane requirement level. At that point, the concentration of the molybdenum in the gasoline can be reduced to about 0.01 to about 10.0 parts per million parts of gasoline.
  • The hydrocarbon fuels to which the molybdenum(VI) compounds can be added comprise hydrocarbons boiling in the gasoline range which range is normally about 20°C-225°C. The base fuel can comprise straight-­chain or branched-chain paraffins, cycloparaffins, olefins, and aromatic compounds or any mixture of such hydrocarbons obtainable from straight-run naphtha, polymeric gasoline, natural gasoline, thermally or catalytically cracked hydrocarbon stocks, alkylate gasoline and catalytically reformed stocks. The fuels can have a research octane number of about 60 to about 100 or preferably about 85 to about 95 for reason of fuel economy and engine performance. The gasoline may also contain conventional gasoline additives such as nonmetallic antiknock compounds, dyes, antioxidants, anti-icing agents, rust inhibitors, detergents, anti-­preignition agents, stabilizers, intake valve deposit control additives and the like. Commonly, gasolines contain a carrier fluid which remains stable and fluid in the induction system and can promote induction system cleanliness by dissolving hydrocarbon soluble deposits. A preferred embodiment of the invention involves the use of a minor amount of methyl t-butyl ether as an antiknock agent.
  • The molybdenum(VI) compounds are effective in lubricant compositions when used in amounts providing about 0.001 to about 5 wt%, preferably about 0.01 to about 2 wt% and more preferably about 0.01 to about 1 wt% of molybdenum(VI) compound based on the oil. Suitable lubricating base oils are mineral oils, petroleum oils, synthetic lubricating oils, and natural lubricating oils of animal or vegetable origin. Concentrates of the additive in appropriate base oils containing about 10 to about 90 weight percent of the additive based on the oil are convenient for producing finished lubricants by dilution with additional base oil. A variety of other additives can be used beneficially with the additives of this invention, including antioxidants, dispersants, corrosion inhibitors, wear inhibitors, friction modifiers, detergents, antibacterial agents, antifoam agents, etc.
  • The gasoline soluble molybdenum compounds are tested for ORI suppression and elevated steady state octane requirement reduction using the CRC E-15 technique with primary reference fuels and full boiling range reference fuels on an engine dynomometer. A GM 3.7 liter (231 cubic inch) V-6, and a Ford 2.3 liter (140 cubic inch) 4-cylinder in-line engine were connected to a load dynomometer. The fuel line is connected via a valve to a test fuel containing various concentrations of molybdenum compound and other containers containing standard fuel having known octane numbers. The conditions of the test are as follows: the temperature of the coolant and oil is maintained at 93°C (200°F) ± 6°C (10°F), the temperature of the inlet air was 40°C-49°C (110°F-120°F), and the temperature of the transmission was maintained at 82°C (180°F) ± 6°C (10°F). The air/fuel ratio was held at about stoichiometric, ignition timing and exhaust gas recirculation was maintained at the stock value. The engine was operated on fuel with and without gasoline soluble molybdenum compound for up to 30,000 equivalent miles. At intervals of 4,000 equivalent miles the standard test fuels were burned in the engine to determine the octane requirement of the engine. After the octane requirement was determined the engines were returned to the test fuel.
  • The following are examples of the preparation of gasoline soluble additive compounds used in gasoline and tables of test results displaying the octane requirement activity of molybdenum compounds in the engine. The examples and tables of data are illustra­tive of the invention. Since many embodiments of the invention can be made, the examples and data should not be used to limit the scope of the invention.
  • EXAMPLE I
  • Into a 3-liter, three-neck flask equipped with a mechanical stirrer, thermometer, temperature control assembly, and an addition funnel and condenser on a side arm adapter was charged 2 liters of anhydrous dioxane, a slurry of 180 grams (1.55 moles) of anhydrous methyl trimethyl acetate, and 144 grams (3.0 moles) of a 50 percent oil dispersion of sodium hydride. The mixture was stirred and heated to reflux and 160 grams (1.60 moles) of dry pinacolone (3,3-dimethyl-2-­butanone) and 200 milliliters of anhydrous dioxane were added dropwise to the stirred and heated mixture over a period of 2 hours. After the addition of the pinacolone was complete, the mixture was held at reflux for 5.5 hours. From the mixture hydrogen gas was evolved. The reaction mixture was chilled in an ice bath and 360 milliliters of concentrated hydrochloric acid were cautiously added to the cold mixture. The resulting acidified mixture was poured into a 6-liter separatory funnel containing 1 liter of water and was extracted with 700 milliliters of pentane. The pentane phase was repeatedly washed with water, dried over magnesium sulfate, and distilled to 93°C to remove pentane. Crude 2,2,6,6-tetramethylheptane-3,5-dione (THDH) (260.7 grams) in oil was recovered. This procedure was repeated three times and the preparations were combined and fractionally distilled to recover 531.6 grams of THDH.
  • EXAMPLE II
  • Into a 250 milliliter Erlenmeyer flask attached to a reflux condenser was charged a slurry of 50.0 grams (0.29 moles) of 2,2,6,6-tetramethyl-3,5-heptane­dione (THDH) and 9.8 grams (0.09 moles) of molybdenum trioxide (MoO₃). The mixture was stirred magnetically and was heated to reflux for 20 hours. The amber colored solution was filtered and upon standing changed to a blue-green solution. The mixture contained 11.5 wt. % molybdenum. Crystals of cis-dioxobis(dipivaloyl­methanato)molybdenum(VI) or MoO₂(THD)₂ were recovered upon slow evaporation of the excess ketone.
  • EXAMPLE III
  • Into a 500 milliliter Erlenmeyer flask equipped with a distillation trap and condenser was charged a slurry of 138 grams (0.75 moles) of 2,2,6,6-tetramethyl-­3,5-heptanedione (THDH) and 27.0 grams (0.188 moles) of MoO₃. The mixture was stirred and was heated on a hot plate to reflux. The mixture was allowed to react for a period of 25.5 hours while 5.0 milliliters of water were azeotropically removed from the reaction mixture (1.48 moles of water per mole of molybdenum trioxide). The dark red brown solution was filtered hot. The filtrate solidified to a dark brown mass upon standing. The recovered substance was identified as trioxotetra(dipivaloylmethanato)dimolybdenum(V,VI) by IR and NMR spectra and also by ESCA spectra of the product from a similar preparation.
  • EXAMPLE IV
  • Into a 500 milliliter Erlenmeyer flask equipped with a distillation trap and condenser assembly was charged a slurry of 36.4 grams (0.25 moles) of MoO₃ and 196.1 grams (1.06 moles) of THDH. The mixture was stirred magnetically and heated to reflux tempera­ture. After 18.5 hours, 6.0 milliliters of water were azeotropically removed (1.32 moles of water per mole of molybdenum trioxide). The reaction mixture was centrifuged and the centrifugate solidified upon standing. The reaction product contained both molyb­denum(VI) and molybdenum(V) chelate as shown by a singlet M-O absorbance and a doublet O-Mo-O absorbance in the IR spectrum.
  • EXAMPLE V
  • Into a 500 milliliter Erlenmeyer flask equipped with a condenser assembly and distillation trap was charged a slurry of 9.8 grams (0.7 moles) of molybdenum trioxide and 50 grams (0.27 moles) of THDH. The mix­ture was stirred mechanically and was heated to reflux for 14.5 hours. 1.6 milliliters of water were azeo­tropically removed (1.31 moles of water per mole of molybdenum trioxide). The THDH in the distillation trap was returned to the reaction mixture, and the mixture was then stripped in vacuum of excess THDH. The resulting product was recrystallized from ethanol. Trans-dioxo(dipivaloylmethanato)molybdenum(VI) chelate (3.2 grams) was recovered as a first crop from the more solublecis isomer.
  • EXAMPLE VI
  • Into a 5-liter, three-neck flask equipped with a mechanical stirrer, thermometer, gas-sparge assembly, side arm adapter and dropping funnel and distillation trap condenser was charged a mixture of 110.0 grams (5.0 moles) of nonylphenol and 150.3 grams (2.5 moles) of ethylenediamine. The mixture was stirred and heated to a temperature of 93°C under a nitrogen atmosphere. To this stirred and heated mixture was added 405.8 grams (5.0 moles) of 37 wt% aqueous formaldehyde solu­tion. The mixture was stirred and reacted for 0.5 hour at 93°C. Volatiles were removed from the reaction mixture by stripping with nitrogen over 75 minutes at 121°C. The resulting product was filtered through celite.
  • Into a 500 ml, three-neck flask equipped with a mechanical stirrer, thermometer, sparge assembly, side arm adapter and dropping funnel, distillation trap and condenser assembly was charged 104.8 grams (0.2 mole) of the above reaction product, 28.8 grams (0.2 mole) molybdenum trioxide and 100 milliliters of xylene. The mixture was stirred and heated to 149°C. Water was removed azeotropically with a nitrogen stream. After 30 minutes at 149°C, 3.6 milliliters of water were removed. The product was filtered through celite and isolated by stripping to 149°C with nitrogen. The dark brown product, which solidified on cooling, contained 11.8 wt% molybdenum and was identified as dioxo-N,Nʹ-(2-oxo-4-nonylbenzyl)ethylenediamino­molybdenum(VI).
  • EXAMPLE VII
  • To a 500 milliliter Erlenmeyer flask equipped with a magnetic stirrer and heater was charged 54 grams of molybdic oxide (MoO₃), 106 grams of water and 22.5 grams of 28 percent aqueous ammonia. The mixture was stirred and heated until dissolution. The ammonium and molybdate product was charged to a 3-liter 3-neck flask equipped with a reflux condenser, water trap, dropping funnel and gas inlet tube containing 500 milliliters of normal heptane and 100 grams of a Mannich product comprising the reaction product of a polyisobutylene substituted phenol having a molecular weight of about 950, paraformaldehyde and diethylenetriamine and oleic acid. The mixture was stirred and heated at reflux for 4.25 hours. Water of reaction was removed by azeotropic distillation, and the mixture was centrifuged. The product was filtered and stripped of heptane by heating to 138°C with a nitrogen stream. The product contained 2.2 wt% molybdenum, 1.31 wt% nitrogen, and had a 40°C viscosity of 2516 SSU.
    Figure imgb0004
    Figure imgb0005
  • An examination of Tables I and II shows that only molybdenum(VI) compounds provide measurable suppression of ORI or reduction of elevated steady state octane requirement.
  • In the initially clean engines (Table I) only the Mo(VI)THD, the Mo(VI)Mannich and the Mo(VI)octoate provided measurable octane requirement increase sup­pression. The mixed Mo(V-VI)THD at 3 ppm and 6 ppm failed to give any measurable suppression.
  • In initially dirty engines (Table II) only the Mo(VI)octoate provided reduction of elevated steady state octane requirement. The Mo(V-VI)THD provided no measurable benefit.

Claims (9)

1. A gasoline fuel composition comprising a major proportion of a liquid hydrocarbon fuel of gasoline boil­ing range in combination with a molybdenum(VI) compound which is soluble in said hydrocarbon fuel, wherein the amount of said molybdenum(VI) compound is from about 0.1 to about 20.0 parts per one million parts of hydrocarbon fuel, said fuel composition is substantially free of metals other than molybdenum, and said molybdenum(VI) com­pound is selected from the group consisting of molybdenum(VI) sulfonates, molybdenum(VI) diamine com­plexes wherein the diamine ligand is of the formula R⁴R⁵N-(CR⁴R⁵)n-NR⁴R⁵ where n is an integer from 1 to 20 and each R⁴ and R⁵ is independently selected from the group consisting of hydrogen and alkyl of 1 to 20 carbon atoms, and molybdenum(VI) compounds which are free of nitrogen, sulfur, and phosphorus.
2. A gasoline fuel composition comprising a major proportion of a liquid hydrocarbon fuel of gasoline boil­ing range in combination with a molybdenum(VI) compound which is soluble in said hydrocarbon fuel, wherein the amount of said molybdenum(VI) compound is sufficient to provide from about 0.01 to about 10 parts of molybdenum per million parts of said hydrocarbon fuel, said fuel com­position is substantially free of metals other than mol­ybdenum, and said molybdenum(VI) compound is selected from the group consisting of molybdenum(VI) sulfonates, molybdenum(VI) diamine complexes wherein the diamine ligand is of the formula R⁴R⁵N-(CR⁴R⁵)n-NR⁴R⁵ where n is an integer from 1 to 20 and each R⁴ and R⁵ ently selected from the group consisting of hydrogen and alkyl of 1 to 20 carbon atoms, and molybdenum(VI) com­pounds which are free of nitrogen, sulfur, and phosphorus.
3. A gasoline fuel composition comprising a major proportion of a liquid hydrocarbon fuel of gasoline boil­ing range in combination with a molybdenum(VI) compound which is soluble in said liquid hydrocarbon fuel, wherein the amount of said molybdenum(VI) compound is effective to reduce elevated steady state octane requirement in a spark ignition internal combustion engine, said fuel composition is substantially free of metals other than molybdenum, and said molybdenum(VI) compound is selected from the group consisting of molybdenum(VI) sulfonates, molybdenum(VI) carboxylates, molybdenum(VI) salts of naphthenic acids, molybdenum(VI) phenates, molybdenum(VI) alkoxides, molybdenum(VI) aryloxides, molybdenum VI beta-diketone compounds, and molybdenum(VI) diamine complexes wherein the diamine ligand is of the formula R⁴R⁵N-(CR⁴R⁵)n-NR⁴R⁵ where n is an integer from 1 to 20 and each R⁴ and R⁵ is independently selected from the group consisting of hydrogen and alkyl of 1 to 20 carbon atoms.
4. A composition as claimed in Claim 2 or Claim 3 wherein said molybdenum (VI) compound is a molybdenum (VI) beta-diketone complex.
5. A composition as claimed in any preceding claim wherein the amount of said molybdenum (VI) compound is sufficient to provide from about 10 to about 1,000 parts of molybdenum per million parts of said hydrocarbon fuel.
6. A composition as claimed in any preceding claim which additionally comprises a minor amount of methyl t-butyl ether which is effective to reduce knock in a spark ignition internal combustion engine.
7. A method for reducing elevated steady state octane requirement in a spark ignition internal combustion engine and maintaining the resulting reduced steady state octane requirement which comprises operating said engine on a first gasoline fuel composition until a reduced steady state octane requirement is achieved and maintain­ing said reduced steady state octane requirement by oper­ating the engine on a second gasoline fuel composition, wherein said first fuel comprises a major proportion of a liquid hydrocarbon fuel of gasoline boiling range in com­bination with an amount of a soluble molybdenum(VI) com­pound which is sufficient to provide from about 10 to about 1,000 parts of molybdenum per million parts of liquid hydrocarbon fuel, wherein said second fuel com­prises a major proportion of a liquid hydrocarbon fuel of gasoline boiling range in combination with an amount of a soluble molybdenum(VI) compound which is sufficient to provide from about 0.01 to about 10 parts of molybdenum per million parts of liquid hydrocarbon fuel, and wherein both of said first and second fuels are substantially free of lead, said molybdenum(VI) compound being selected from the group consisting of molybdenum(VI) sulfonates, molybdenum(VI) diamine complexes wherein the diamine ligand is of the formula R⁴R⁵N-(CR⁴R⁵)n-NR⁴R⁵ where n is an integer from 1 to 20 and each R⁴ an R⁵ is independ­ently selected from the group consisting of hydrogen and alkyl of 1 to 20 carbon atoms, and molybdenum(VI) com­pounds which are free of nitrogen, sulfur, and phosphorus.
8. A method for suppressing octane requirement increase in a spark ignition internal combustion engine which comprises operating said engine with the gasoline fuel composition which is set forth in any of Claims 1 to 6.
9. A method for reducing elevated steady state octane requirement in a spark ignition internal combustion engine having an increased octane requirement of about 2 to about 7 units after operation with gasoline substan­tially free of lead and molybdenum which comprises operat­ing said engine with a gasoline fuel composition comprising a major proportion of a liquid hydrocarbon fuel of gasoline boiling range in combination with a molybdenum(VI) compound which is soluble in said hydrocar­bon fuel, wherein the amount of said molybdenum(VI) com­pound is sufficient to provide from about 10 to about 1,000 parts of molybdenum per million parts of said hydro­carbon fuel, and the amount of said gasoline fuel composi­tion is effective to reduce said elevated steady state octane requirement by at least about 20%, said molybdenum(VI) compound being selected from the group con­sisting of molybdenum(VI) sulfonates, molybdenum(VI) dia­mine complexes wherein the diamine ligand is of the formula R⁴R⁵N-(CR⁴R⁵)n-NR⁴R⁵ where n is an integer from 1 to 20 and each R⁴ and R⁵ is independently selected from the group consisting of hydrogen and alkyl of 1 to 20 carbon atoms, and molybdenum(VI) compounds which are free of nitrogen, sulfur, and phosphorus.
EP87301344A 1980-09-25 1987-02-17 Gasoline compositions containing hexavalent molybdenum Expired - Lifetime EP0279090B1 (en)

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US06/833,225 US4647293A (en) 1980-09-25 1986-02-24 Gasoline compositions containing hexavalent molybdenum
EP87301344A EP0279090B1 (en) 1987-02-17 1987-02-17 Gasoline compositions containing hexavalent molybdenum
AT87301344T ATE69835T1 (en) 1987-02-17 1987-02-17 GASOLINE COMPOSITIONS CONTAINING HEXAVAL MOLYBDENUM.
DE8787301344T DE3774868D1 (en) 1987-02-17 1987-02-17 HEALTHY MOLYBDAIC GASOLINE COMPOSITIONS.

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GB770278A (en) * 1954-04-30 1957-03-20 Exxon Research Engineering Co Fuel composition
US2881062A (en) * 1955-08-17 1959-04-07 Tide Water Associated Oil Comp Hydrocarbon fuel
US3064024A (en) * 1958-12-08 1962-11-13 Ethyl Corp Cycloheptatrienyl cycloheptatriene metal compounds and process of making the same
US3093671A (en) * 1960-11-14 1963-06-11 Ethyl Corp Cyclic diene group vi-beta metal carbonyls
GB950147A (en) * 1960-12-30 1964-02-19 Shell Int Research Fuel compositions
US3124600A (en) * 1964-03-10 Organometallic compounds
US3168368A (en) * 1960-04-27 1965-02-02 Air Prod & Chem Method of treating exhaust gases of internal combustion engines
US3282838A (en) * 1960-05-10 1966-11-01 Texaco Inc Petroleum liquids containing amine salts of molybdic acid
US3755195A (en) * 1968-12-20 1973-08-28 Ethyl Corp Spark plug anti-foulant
FR2187891A1 (en) * 1972-06-14 1974-01-18 Continental Oil Co Oil sol metal sulphonate prepn - contg an amine
GB2064548A (en) * 1979-11-23 1981-06-17 Lubrizol Corp Molybdenum-containing compositions and lubricants and fuels containing them
EP0049094A1 (en) * 1980-09-25 1982-04-07 Amoco Corporation Hydrocarbon-soluble polyamine-molybdenum compositions
GB2089431A (en) * 1980-12-06 1982-06-23 Weir Pumps Ltd Preventing Surge in Pumps
US4647293A (en) * 1980-09-25 1987-03-03 William H. Magidson Gasoline compositions containing hexavalent molybdenum

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3124600A (en) * 1964-03-10 Organometallic compounds
FR823791A (en) * 1936-07-13 1938-01-26 Leo Corp Method for operating an internal combustion engine
GB770278A (en) * 1954-04-30 1957-03-20 Exxon Research Engineering Co Fuel composition
US2881062A (en) * 1955-08-17 1959-04-07 Tide Water Associated Oil Comp Hydrocarbon fuel
US3064024A (en) * 1958-12-08 1962-11-13 Ethyl Corp Cycloheptatrienyl cycloheptatriene metal compounds and process of making the same
US3168368A (en) * 1960-04-27 1965-02-02 Air Prod & Chem Method of treating exhaust gases of internal combustion engines
US3282838A (en) * 1960-05-10 1966-11-01 Texaco Inc Petroleum liquids containing amine salts of molybdic acid
US3093671A (en) * 1960-11-14 1963-06-11 Ethyl Corp Cyclic diene group vi-beta metal carbonyls
GB950147A (en) * 1960-12-30 1964-02-19 Shell Int Research Fuel compositions
US3755195A (en) * 1968-12-20 1973-08-28 Ethyl Corp Spark plug anti-foulant
FR2187891A1 (en) * 1972-06-14 1974-01-18 Continental Oil Co Oil sol metal sulphonate prepn - contg an amine
GB2064548A (en) * 1979-11-23 1981-06-17 Lubrizol Corp Molybdenum-containing compositions and lubricants and fuels containing them
EP0049094A1 (en) * 1980-09-25 1982-04-07 Amoco Corporation Hydrocarbon-soluble polyamine-molybdenum compositions
US4647293A (en) * 1980-09-25 1987-03-03 William H. Magidson Gasoline compositions containing hexavalent molybdenum
GB2089431A (en) * 1980-12-06 1982-06-23 Weir Pumps Ltd Preventing Surge in Pumps

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