Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L10/00—Use of additives to fuels or fires for particular purposes
  • C10L10/10—Use of additives to fuels or fires for particular purposes for improving the octane number
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/1814—Chelates
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
  • C10L1/1828—Salts thereof
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/188—Carboxylic acids; metal salts thereof
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
  • C10L1/2431—Organic compounds containing sulfur, selenium and/or tellurium sulfur bond to oxygen, e.g. sulfones, sulfoxides
  • C10L1/2437—Sulfonic acids; Derivatives thereof, e.g. sulfonamides, sulfosuccinic acid esters
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/26—Organic compounds containing phosphorus
  • C10L1/2633—Organic compounds containing phosphorus phosphorus bond to oxygen (no P. C. bond)
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/30—Organic compounds compounds not mentioned before (complexes)
  • C10L1/305—Organic 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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• 1987
  • 1987-02-17 AT AT87301344T patent/ATE69835T1/de not_active IP Right Cessation
  • 1987-02-17 EP EP87301344A patent/EP0279090B1/fr not_active Expired
  • 1987-02-17 DE DE8787301344T patent/DE3774868D1/de not_active Expired - Fee Related

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