EP0468043A1 - Composition d'additif de carburant. - Google Patents

Composition d'additif de carburant.

Info

Publication number
EP0468043A1
EP0468043A1 EP91905183A EP91905183A EP0468043A1 EP 0468043 A1 EP0468043 A1 EP 0468043A1 EP 91905183 A EP91905183 A EP 91905183A EP 91905183 A EP91905183 A EP 91905183A EP 0468043 A1 EP0468043 A1 EP 0468043A1
Authority
EP
European Patent Office
Prior art keywords
fuel
additive composition
fuel additive
hydrocarbyl
amine
Prior art date
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
Application number
EP91905183A
Other languages
German (de)
English (en)
Other versions
EP0468043B1 (fr
EP0468043A4 (en
Inventor
Thomas F Buckley Iii
David A Kohler
Ralph E Olsen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chevron USA Inc
Original Assignee
Chevron Research and Technology Co
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Publication of EP0468043A1 publication Critical patent/EP0468043A1/fr
Publication of EP0468043A4 publication Critical patent/EP0468043A4/en
Application granted granted Critical
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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
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
    • 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
    • C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
    • 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
    • C10L1/16—Hydrocarbons
    • C10L1/1608—Well defined compounds, e.g. hexane, benzene
    • 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
    • C10L1/16—Hydrocarbons
    • C10L1/1616—Hydrocarbons fractions, e.g. lubricants, solvents, naphta, bitumen, tars, terpentine
    • 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
    • C10L1/16—Hydrocarbons
    • C10L1/1625—Hydrocarbons macromolecular compounds
    • 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
    • C10L1/192—Macromolecular compounds
    • C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
    • C10L1/1981—Condensation polymers of aldehydes or ketones
    • 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
    • C10L1/192—Macromolecular compounds
    • C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
    • C10L1/1985—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid polyethers, e.g. di- polygylcols and derivatives; ethers - 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
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
    • 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
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
    • C10L1/2225—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates hydroxy containing
    • 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
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • C10L1/224—Amides; Imides carboxylic acid amides, imides
    • 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
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • 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
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)
    • 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

Definitions

  • Deposits adversely affect the operation of vehicles using hydrocarbon fuels. For example, deposits on the carburetor throttle body and venturies increase the fuel-to-air ratio of the gas mixture to the combustion chamber thereby increasing the amount of unburned hydrocarbon and carbon monoxide discharged from the chamber. High fuel-to-air ratios also reduce the gas mileage obtainable from the vehicle.
  • the first generation of fuel additives consisted of detergents which helped to maintain the cleanliness of critical carburetor elements. These initial fuel additives were typically used in small doses, generally in the range of 15 to 30 ppm. Unfortunately, these small doses of additive provided little deposit control in other parts of combustion engines.
  • the next generation of fuel additives generally provided improved deposit control in the intake system including intake manifold hotspots, runners, intake valve ports, and intake valves.
  • the extent of deposit control was typically modulated by controlling additive dose, usually in the range of 70 to 2,000 ppm.
  • additive doses increased to high levels, the accumulation of combustion chamber deposits became a significant problem for reasons which will become apparent hereinbelow.
  • each engine when new, requires a certain minimum octane fuel in order to operate satisfactorily without pinging and/or knocking, and/or after run. As the engine is operated on any gasoline, this minimum octane requirement increases. This is apparently caused by formation of deposits in the com- bustion chamber. In most cases, if the engine is operated on the same fuel for a prolonged period, the ORI will reach an equilibrium. Equilibrium is typically reached after 5,000 to 15,000 miles of automobile operation.
  • the ORI problem is compounded by the fact that the most common method for increasing the octane rating of unleaded gasoline is to increase its aromatic content. These aroma- tics, however, eventually cause an even greater increase in the octane requirement. Moreover, some of the nitrogen- containing compounds presently used as deposit-control additives ' and their mineral oil or polymer carriers may also significantly contribute to ORI in engines using unleaded fuels.
  • hydrocarbyl poly(oxyalkylene) aminocarbamate dispersants are commercially successful fuel additives which control induction system deposits without significantly contributing to the ORI problem.
  • these additives are relatively expensive and this discourages their use in high concentrations.
  • hydrocarbyl poly(oxyalkylene) aminocarbamates are not quite as effective at controlling deposits in the injectors or carburetor of modern combustion engines.
  • the performance of these engines, which contain fuel injection fuel delivery systems, can be substantially upset by relatively small amounts of deposits.
  • low molecular weight hydrocarbyl amine an d polyamine detergents are known to effectively control deposits in injectors. These amine detergents are similar to those described earlier that were used to maintain clean carburetors. However, to control deposits on injectors, these detergents are used at fuel concentrations in the range of 40 to 70 ppm. It is now known that such high doses of injector detergents negatively impact the control of deposits on intake valves and in the combustion chamber of engines.
  • An additional problem with some low molecular weight hydrocarbyl amine and polyamine detergents that contain a primary or secondary amine functionality is the formation of a solid precipitate when the amine is exposed to carbon dioxide, such as exposure to the carbon dioxide in air. It is believed that this precipitate is a carbamic acid adduct formed by reaction of the primary or secondary amine with carbon dioxide. Whatever its chemical structure, formation of such a precipitate is undesirable for reasons which will be explained hereinbelow.
  • U.S. Patent No. 4,810,263 to Zimmerman et al. discloses an additive package for reducing and/or preventing fouling in a multiport fuel-injected engine which contains an amine oxide, such as bis(2-hydroxy ethyl) cocamine oxide, and a demulsifier comprising one or more demulsifying agents selected from a fatty acid alkylamine reaction product and a solution of oxyalkylated alkylphenol formaldehyde resins and polyglycols.
  • an amine oxide such as bis(2-hydroxy ethyl) cocamine oxide
  • demulsifier comprising one or more demulsifying agents selected from a fatty acid alkylamine reaction product and a solution of oxyalkylated alkylphenol formaldehyde resins and polyglycols.
  • 4,836,829 to Zimmerman et al discloses a similar addi- tive package which contains a tertiary amine, such as bis(2-hydroxy ethyl) cocamine, preferably in combination with an amine oxide, and a demulsifying agent.
  • a tertiary amine such as bis(2-hydroxy ethyl) cocamine
  • the amine oxide typically has water present from the manufacturing process, which is difficult to completely remove.
  • the amine oxide is commercially available as an isopropyl alcohol solution which contains from 6 to 8 weight percent water.
  • mineral oil carriers are used with either the amine detergents or the hydrocarbyl poly(oxyalkylene) aminocarbamate dispersants to assist in removing and preventing deposits.
  • mineral oil carriers neither group of fuel additives provides complete intake system deposit control.
  • an intake valve and combustion chamber deposit control addi- tive such as a hydrocarbyl poly(oxyalkylene) aminocarbamate dispersant
  • an injector detergent such as a low molecular weight amine or polyamine
  • an effective amount of a carrier fluid to provide a multi-component, multi- functional fuel additive package which maximizes effective control of deposits throughout the entire intake system and combustion chamber of engines, and which itself does not significantly contribute to the octane requirement increase problem.
  • the choice of components for a multi-component, multi-functional deposit control fuel additive composition is not straightforward.
  • the composition must provide effective deposit control at additive levels which are economical, and with additives which do not contribute to ORI. It is also essential that the composition remains homogeneous, i.e., a single liquid phase, under all field conditions, if the composition is to dependably deliver the expected deposit control performance when blended with fuel and in actual engine service.
  • maintaining a single liquid phase is critical.
  • the composition of additive delivered to the fuel will be erratic.
  • phase separation of an incompatible composition can take many forms. Typically, the phase separation appears first as a haze which eventually settles out, either up or down, depending on the relative densities of the two phases. Thus as the level of additive in, for example, a storage tank is drawn down, the interface between the phases may pass below the liquid draw point, at which time the composition of additive flowing into the fuel will change, perhaps drastically.
  • phase separation will also cause serious problems in the additive distribution system which distributes the additive composition to the fuel. If the phase separation involves two liquid phases, the heavier phase will collect on the bottom of the additive storage tank and at the low points of the additive delivery lines. This will result in the need for expensive and inconvenient periodic cleanout of the additive distribution equipment.
  • phase separation involves a solid separating from the bulk liquid additive composition, the effect would be more serious and immediate.
  • Virtually all additive injection S systems have fine-mesh filters to protect the valves and seals in the injection pump. A solid phase would rapidly plug these filters and shut down the injector, thus requiring that the filter be cleaned before restarting the injector.
  • a separate solid phase would also require the periodic cleaning of the additive storage tank. The criticality of a homogeneous additive composition is thus apparent.
  • the demulsifier must exhibit demulsification properties when utilized in motor fuels at relatively low levels, such -as 5 to 25 parts per million.
  • a solvent or diluent in the additive composition.
  • the primary function of this component is to reduce the low-temperature viscosity of the composition.
  • the solvent must however be compatible with the additive components and economical.
  • U.S. Patent Nos. 4,160,648 and 4,191,537 disclose hydrocarbyl poly(oxyalkylene) aminocarbamates as fuel additives.
  • the use of a fuel-soluble carrier oil and, additionally, a demulsifier in combination with the hydrocarbyl poly(oxyalkylene) aminocarbamates is also disclosed.
  • U.S. Patent Nos. 3,898,056 and 3,960,515 disclose a mixture of high and low molecular weight hydrocarbyl amines used as detergents and dispersants at low concentrations in fuels.
  • the high molecular weight hydrocarbyl amine contains at least one hydrocaryl group having a molecular weight from about 1,900 to 5,000 and the low moleciilar weight hydro- carbyl amine contains at least one hydrocarbyl group having a molecular weight from about 300 to 600.
  • the weight ratio of low molecular weight amine to high molecular weight amine in the mixture is maintained between about 0.5:1 and 5:1.
  • the present invention provides a novel homogeneous fuel additive composition which comprises:
  • a dispersant comprising a hydrocarbyl poly(oxyalkylene) aminocarbamate having at least one basic nitrogen atom and an average molecular weight of about 1,000 to about 3,000;
  • an injector detergent comprising a branched-chain hydrocarbyl amine having at least one basic nitrogen atom and an average molecular weight of about 300 to about 700, wherein the hydrocarbyl moiety is derived from polymers of C 2 to C g olefins;
  • the present invention further provides a fuel composition comprising a hydrocarbon boiling in the gasoline or diesel range and from about 400 to 1,200 parts per million of the homogeneous fuel additive composition described above.
  • the present invention is also concerned with a fuel concentrate comprising an inert stable oleophilic organic solvent boiling in the range of 150° to 400°F and from about 5 to 50 weight percent of the homogeneous fuel additive composition of the invention.
  • the present invention is based on the surprising discovery that the unique combination of dispersant, low molecular weight injector detergent, demulsifier and carrier fluid described herein provides com- plete intake deposit control while minimizing debilitating combustion chamber deposits, which correlate to ORI.
  • a low molecular weight branched chain hydrocarbyl amine as an injector detergent avoids the precipitation problem -associated with known amine deter- gents, such as oleyl amine.
  • the present invention addresses the problem associated with the fact that none of the prior art fuel additives can singly, or in typical use concentration com- binations, provide complete gasoline intake system deposit control.
  • the instant invention demonstrates a new formulat- ing technology which provides maximum deposit control in each critical deposit forming area while at the same time minimizing the doses of each critical ingredient. As a consequence, it is now possible to minimize the negative impact of each individual ingredient upon overall intake system and combustion chamber deposit control performance.
  • the instant invention describes a fuel additive composition which provides a homogeneous mixture of deposit control additives and carrier fluid, in individual proportions significantly below the levels historically recognized for maintaining adequate intake system deposit control in their respective areas of effectiveness, and an oil compatible demulsifier. /XL Accordingly, the novel fuel additive composition of the present invention is a homogeneous mixture which comprises the following components:
  • a dispersant comprising a hydrocarbyl poly(oxyalkylene) aminocarbamate having at least one basic nitrogen atom and an average molecular weight of about 1,000 to about 3,000;
  • an injector detergent comprising a branched-chain hydrocarbyl amine having at least one basic nitrogen atom and an average molecular weight of about 300 to about 700, wherein the hydrocarbyl moiety is derived from polymers of C ⁇ to C ⁇ olefins;
  • the homogeneous fuel additive composition of the invention will contain about 10 to 70 weight percent of the aminocarbamate dispersant, about 1 to 10 weight percent of the hydrocarbyl amine injector detergent, about 0.5 to 5 weight percent of the fuel demulsifier and about 25 to 80 weight percent of the carrier fluid.
  • the present fuel additive composition can be used neat, it is often desirable to dilute the composition with an inert solvent or diluent, up to about 50 percent dilution.
  • the dispersant employed in the homogeneous fuel additive composition of the invention is a hydrocarbyl ⁇ 3 poly(oxyalkylene) aminocarbamate having at least one basic nitrogen atom and an average molecular weight of about 1,000 to 3,000.
  • the dispersant employed can be said to contain a poly(oxyalkylene) component, an amine component and a carbamate connecting group.
  • the hydrocarbyl-terminated poly(oxyalkylene) polymers which are utilized in preparing the carbamates of the present invention are monohydroxy compounds, e.g., alcohols, often termed monohydroxy polyethers, or polyalkylene glycol monocarbyl ethers, or "capped" poly(oxyalkylene) glycols, and are to be distinguished from the poly(oxyalkylene) glycols (diols), or polyols, which are not hydrocarbyl-terminated, i.e., are not capped.
  • the hydrocarbyl-terminated poly(oxyalkylene) alcohols are produced by the addition of lower alkylene oxides, such as oxirane., ethylene oxide, propylene oxide, butylene oxide, etc.
  • R is the hydrocarbyl group which caps the poly(oxyalkylene) chain.
  • the group R will generally contain from 1 to about 30 carbon atoms, preferably from 2 to about 20 carbon atoms and is preferably aliphatic or aromatic, i.e., an alkyl or alkyl phenyl wherein the alkyl is a straight or branched-chain of from 1 to about 24 carbon atoms.
  • R is alkylphenyl wherein the alkyl group is a branched-chain of 12 carbon atoms, derived from propylene tetramer, and commonly referred to as tetraprop ⁇ nyl.
  • the oxyalkylene units in the poly(oxyalkylene) component preferably contain from 2 to about 5 carbon atoms but one or more units of a i t larger carbon number may also be present.
  • the poly(oxyalkylene) component employed in the present invention is more fully described and exemplified in U.S. Patent No. 4,191,537, the disclosure of which is incorporated herein by reference.
  • hydrocarbyl group on the hydrocarbyl poly(oxyalkylene) component will preferably contain from 1 to about 30 carbon atoms, longer hydrocarbyl groups, particularly longer chain alkyl phenyl groups, may also be employed.
  • alkylphenyl poly(oxyalkylene) aminocarbamates wherein the alkyl group contains at least 40 carbon atoms are also contemplated for use in the present invention.
  • the alkyl phenyl group on the aminocarbamates of U.S. Patent No. 4,881,945 will pre- ferably contain an alkyl group of 50 to 200 carbon atoms, and more preferably, an alkyl group of 60 to 100 carbon atoms.
  • the disclosure of U.S. Patent No. 4,881,945 is incorporated herein by reference.
  • the amine moiety of the hydrocarbyl-terminated poly(oxyalkylene) aminocarbamate is preferably derived from a polyamine having from 2 to about 12 amine nitrogen atoms and from 2 to about 40 carbon atoms.
  • the polyamine is preferably reacted with a hydrocarbyl poly- (oxyalkylene) chloroformate to produce the hydrocarbyl poly(oxyalkylene) aminocarbamate fuel additive finding use within the scope of the present invention.
  • the chloroformate is itself derived from hydrocarbyl 15 poly(oxyalkylene) alcohol by reaction with phosgene.
  • the polyamine encompassing diamines, provides the product poly(oxyalkylene) aminocarbamate with, on the average, at least about one basic nitrogen atom per carbamate molecule, i.e., a nitrogen atom titratable by strong acid.
  • the polyamine preferably has a carbon-to- nitrogen ratio of from about 1 1 to about 10:1.
  • the polyamine may be substituted with substituents selected from hydrogen, hydrocarbyl groups of from 1 to about 10 carbon atoms, acyl groups of from 2 to about 10 carbon atoms, and monoketone, monohydroxy, mononitro, mono- cyano, alkyl and alkoxy derivatives of hydrocarbyl groups of from 1 to 10 carbon atoms. It is preferred that at least one of the basic nitrogen atoms of the polyamine is a primary or secondary amino nitrogen.
  • the polyamine component employed in the present invention has been described and exemplified more fully in U.S. Patent No. 4,191,537.
  • Hydrocarbyl as used in describing the hydrocarbyl poly(oxyalkylene) and amine components used in this invention, denotes an organic radical composed of carbon and hydrogen which may be aliphatic, alicyclic, aromatic or combinations thereof, e.g., aralkyl.
  • the hydrocarbyl group will be relatively free of aliphatic unsaturation, i.e., ethylenic and acetylenic, particu- larly acetylenic unsaturation.
  • polyalkylene polyamine including alkylene- diamine, and including substituted polyamines, e.g., alkyl and hydroxyalkyl-substituted polyalkylene poly- amine.
  • the' alkylene group contains from 2 to 6 carbon atoms, there being preferably from 2 to 3 carbon atoms between the nitrogen atoms. Examples of /(,
  • polyamines include ethylenediamine, diethylene tri-
  • compositions of the present invention is obtained by:
  • -_ hydroxyl oxygen of the poly(oxyalkylene) alcohol component, and the carbonyl group -C(O)- is preferably
  • a coupling agent e.g., phosgene.
  • the hydrocarbyl 26 poly(oxyalkylene) alcohol is reacted with phosgene to 27 produce a chloroformate and the chloroformate is reacted 28 with the polyamine.
  • the carbamate linkages are formed 29 as the poly(oxyalkylene) chains are bound to the 30 nitrogen of the polyamine through the oxycarbonyl group 31 of the chloroformate.
  • the aminocarbamate 34 contains at least one hydrocarbyl poly(oxyalkylene) polymer chain bonded through an oxycarbonyl group to a nitrogen atom of the polyamine, but the carbonate may contain from 1 to 2 or more such chains.
  • the hydrocarbyl poly(oxyalkylene) amino- carbamate product contains on the average, about 1 poly(oxyalkylene) chain per molecule (i.e., is a monocarbamate) , although it is understood that this reaction route may lead to mixtures containing appreciable amounts of di or higher poly(oxyalkylene) chain substitution on a polyamine containing several reactive nitrogen atoms.
  • a particularly preferred aminocarbamate is alkylphenyl poly(oxybutylene) amino- carbamate, wherein the amine moiety is derived from ethylene diamine or diethylene triamine.
  • the injector detergent employed in the homogeneous fuel additive composition of the present invention is a branched-chain hydrocarbyl amine having at least one basic nitrogen atom and an average molecular weight of about 300 to about 700, and wherein the hydrocarbyl moiety is derived from polymers of C, to C, olefins.
  • the branched-chain hydrocarbyl group will ordinarily be prepared by polymer- izing olefins of from 2 to 6 carbon atoms (ethylene being copolymerized with another olefin so as to provide a branched-chain).
  • the branched chain hydrocarbyl group will generally have at least 1 branch per 6 carbon atoms along n the chain, preferably at least 1 branch per 4 carbon atoms along the chain and, more preferably, at least 1 branch per 2 carbon atoms along the chain.
  • the preferred branched- chain hydrocarbyl groups are polypropylene and polyiso- butylene.
  • the branches will usually be of from 1 to 2 carbon atoms, preferably 1 carbon atom, that is, methyl. In general, the branched-chain hydrocarbyl group will contain from about 20 to 40 carbon atoms.
  • the branched-chain hydrocarbyl amines are not a pure single product, but rather a mixture of compounds having an average molecular weight. Usually, the range of molecular weights will be relatively narrow and peaked near the indicated molecular weight.
  • the amino component of the branched-chain hydrocarbyl amines may be either a monoamine or a polyamine.
  • the monoamine or polyamine component embodies a broad class of amines having from 1 to 10 amine nitrogen atoms and from 2 to 40 carbon atoms with a carbon to nitrogen ratio between about 1:1 and 10:1. in most instances, the amine component is not a pure single product, but rather a mixture of compounds having a major quantity of the designated amine.
  • the compositions will be a mixture of amines having as the major product the compound indicated and having minor amounts of analogous compounds.
  • the amine component when it is a polyamine, it will preferably be a polyalkylene polyamine, including alkylenedia ine.
  • the alkylene group will contain from 2 to 6 carbon atoms, more preferably from 2 to 3 carbon atoms.
  • Examples of such polyamines include ethylene diamine, diethylene triamine, triethylene tetramine and tetraethylene penta ine. rt ⁇
  • a particularly preferred branched-chain hydrocarbyl amine is polyisobutenyl ethylene diamine.
  • branched-chain hydrocarbyl amine injector detergents employed in the fuel additive composition of the invention are prepared by conventional procedures known in the art. Such branched-chain hydrocarbyl amines and their prepa- rations are described in detail in U.S. Patent Nos. 3,438,757; 3,565,804; 3,574,576; 3,848,056 and 3,960,515, the disclosures of which are incorporated herein by reference.
  • the demulsifier employed in the fuel additive composition of the invention is a chemical agent which, when used in relatively low concentrations in gasoline compositions, will promote the rapid coalescence of emulsified water to the point where it can be effectively removed from the bulk hydrocarbon by means of static gravity assisted separation in a quiescent storage tank.
  • the demulsifier agent is frequently a mixture of several chemical agents which in proper combination afford the desired demulsifying charac- teristics. These agents are typically selected from, but are not restricted to, alkylphenol resins, polyoxyalkylene- based fluids, alkylarylsulfonates, derivatives of fatty acids, and the like.
  • One preferred demulsifier for use in the composition of this invention is known as Tolad ⁇ ' T-326, a commercially available demulsifier from Petrolite Corporation, Tretolite Division, St. Louis, Missouri, which comprises a mixture of oxyalkylated alkylphenol-formaldehyde resins, polyoxyalkylene glycols, and sodium arylsulfonate in heavy aromatic naphtha.
  • Tolad ⁇ ' T-326 a commercially available demulsifier from Petrolite Corporation, Tretolite Division, St. Louis, Missouri, which comprises a mixture of oxyalkylated alkylphenol-formaldehyde resins, polyoxyalkylene glycols, and sodium arylsulfonate in heavy aromatic naphtha.
  • the fuel additive com- position of this invention being generally regarded as a dispersant agent, also has the tendency to promote emulsion formation when gasoline compositions containing the additive composition are contacted with water.
  • Demulsifiers at relatively low fuel concentrations, assist in the demulsifi- cation of such emulsions and thereby help to clarify other- wise cloudy wet fuels. It is important to note that demulsifiers, when used in concentrations higher than about 25 ppm, can also promote emulsification. Hence, their dosage must be carefully regulated and adjusted to the physical/chemical characteristics of fuel compositions containing the fuel additive components. Many demulsifiers will satisfy this criterion but will nevertheless fail the criterion of compatibility with the other components of the fuel additive composition.
  • the carrier fluid employed in this invention is a chemically inert hydrocarbon-soluble liquid vehicle which substantially increases the nonvolatile residue (NVR), or solvent-free liquid fraction of the fuel additive composition while not overwhelmingly contributing to octane requirement increase.
  • the carrier fluid may be a natural or synthetic oil, such as mineral oil, refined petroleum oils, synthetic polyalkanes and alkenes, synthetic polyoxyalkylene derived oils, and the like, as described, for example, in U.S. Patent No. 4,191,537 to Lewis. These carrier fluids are believed to act as a carrier for the dispersant and detergent and to assist in removing and retarding deposits.
  • the carrier fluid employed in the instant invention must also be capable of forming a homogeneous mixture with the other components of the present fuel additive composition.
  • suitable carrier fluids include Chevron Neutral Oil 500R and Chevron Neutral Oil 600P, available from Chevron U.S.A. Inc., San Francisco, California.
  • the fuel additive composition of the present invention will generally be employed in a hydrocarbon distillate fuel boiling in the gasoline or diesel range.
  • the proper concen- tration of this additive composition necessary in order to achieve the desired detergency and dispersancy varies depending upon the type of fuel employed, the presence of other additives, and the like. In general, however, from about 400 to 1,200 parts per million (ppm) of the instant fuel additive composition in the base fuel is needed to achieve the best results.
  • fuel compositions containing the homogeneous fuel additive composition of the invention will generally contain about 100 to 225 ppm of the aminocarbamate dispersant, about 10 to 70 ppm of the hydrocarbyl amine injector detergent, about 5 to 25 ppm of the demulsifier and about 250 to 800 ppm of the carrier fluid.
  • the deposit control fuel additive composition of the present invention may also be formulated as a concentrate, using an inert, stable oleophilic organic solvent boiling in the range of about 150° to 400°F.
  • an aliphatic or an aromatic hydrocarbon solvent is used, such as benzene, toluene, xylenes, or higher-boiling aromatics or aromatic thinners.
  • Aliphatic alcohols of about 3 to 8 carbon atoms, such as isopropanol, isobutylcarbinol, n-butanol, and the like, in combination with hydrocarbon solvents are also suitable for use with the additive composition of the invention.
  • the amount of the instant additive composition will be ordinarily at least 5 percent by weight and generally not exceed 50 percent by weight, preferably from 10 to 30 weight percent.
  • antiknock agents e.g., methylcyclopentadienyl manganese tricarbonyl, tetramethyl or tetraethyl lead, tert- butyl methyl peroxide and various oxygenates, such as methanol, ethanol and methyl t-butyl ether.
  • lead scavengers such as aryl halides, e.g., dichloro- benzene or alkyl halides, e.g., ethylene dibromide. Addi- tionally, antioxidants and metal deactivators may be present.
  • diesel fuels other well-known additives can be employed such as pour point depressants, flow improvers, cetane improvers, etc.
  • a dispersant useful in this invention was prepared in a manner similar to that described in Lewis, U.S. Patent No. 4,160,648, Examples 6-8, except that diethylene triamine was used in place of ethylene diamine.
  • a tetrapropenyl phenol was reacted stepwise with butylene oxide, phosgene, and diethylene triamine to afford a high molecular weight tetrapropenyl poly(oxybutylene) aminocarbamate, referred to hereinrjelow as a polyether amine (PEA) .
  • PEA polyether amine
  • An injector detergent (ID) was prepared in a manner similar to that described by Honnen, U.S. Patent No. 3,438,757, Example 2.
  • a C,» polyisobutene having a molecular weight of approximately 420 was reacted stepwise with chlorine and ethylene diamine to produce a polyisobutene ethylene diamine adduct.
  • Chevron Neutral Oil 500R and Chevron Neutral Oil 600P were used as carrier fluids (CF) in the examples hereinbelow.
  • Chevron Neutral Oil 500R is a highly refined base oil having a pour point of -12 ⁇ C (Max.) and a viscosity of 98.6 cSt at 40°C.
  • Chevron Neutral Oil 600P is a highly refined base oil having a pour point of 10°F (-12.2°C) and a viscosity of 129.5 cSt at 37.8°C.
  • the demulsifier (D) used in these examples to illustrate the present invention was a commercially available demulsifier (from Petrolite Corporation, Tretolite Division, St. Louis, MO) identified by the manufacturer as Tolad ⁇ T-326.
  • This demulsifier comprises a mixture of oxyalkylated alkylphenol- formaldehyde resins, polyoxyalkylene glycols, and sodium arylsulfonate (1 to 5 weight percent) in heavy aromatic naphtha (30 to 60 weight percent).
  • Tolad ® T-326 is reported to have a flash point, SFCC, of 114°F, a pour point, ASTM D-97, of 5°F, and a viscosity of 263 SUS at 60°F.
  • Two fuel additive compositions were prepared. 150 parts of the polyether amine of Ex. 1, 25 parts of the injector detergent of Ex. 2, 12 parts of a demulsifier, 212 parts of Chevron Solvent 25, (which is a mixture of C-9 blending aromatics available from Chevron U.S.A. Inc., San Francisco, California) and 450 parts of Chevron, Neutral Oil 500R (Ex. 3) were mixed at room temperature with stirring in a 200 ml flask. t
  • Sample 6A contained Tolad v -—' T-326 (as described in Ex. 4) as the demulsifier.
  • Sample 6B contained L-1562 as the demulsi- fier.
  • L-1562 is a commercially available demulsifier pur- chased from Petrolite Corporation, St. Louis, MO.
  • a third additive composition, Sample 6C, contained oleyl amine as the injector detergent, and is shown for comparison pur- poses.
  • Oleyl amine is a low molecular weight straight chain C.g primary amine.
  • the compatibility test used was a modification of the procedure described by ASTM Method D-2273, except that, since a significant amount of diluent solvent (Chevron Solvent 25, a mixture of C-9 blending aromatics) was already present in these compositions, this test was performed with- out further dilution. The test was performed in two parts. In Part A, the samples prepared by the procedure of Example 6 were held at ambient or room temperature (about 20-25°C) for 24 hours. Each sample was then visually inspected for a secondary phase. If a secondary phase was observed, the sample was centrifuged and the volume percent of the secondary phase determined. If no secondary phase was observed. Part B of this test was performed.
  • Part B the samples were cooled to 0°F and held at this temperature for 24 hours. Each sample was then visually inspected for a secondary phase. If a secondary phase was observed, the sample was centrifuged and the volume percent of the secondary phase determined.
  • the fuel additive composition of this invention does not have any measurable volume percent of a secondary phase under these test conditions. However, when L-1562 was used as the demulsifier (Sample 6B), or when oleyl amine was used as the injector detergent (Sample 6C), significant and unacceptable levels of a secondary phase were observed.
  • Sample 6C 150 parts , EA (Ex 1) ⁇ 0.005 0.05
  • Sample 6C containing oleyl amine as an injector detergent, was centrifuged after cooling to 0°F and showed a small volume (0.05 vol.%) of an insoluble solid sediment. Thus it failed the criterion that sediment levels must not exceed 0.005 vol.%.

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

Abstract

Composition d'additif de carburant homogène comprenant : (a) un dispersant comprenant un hydrocarbyle poly(oxyalkylène) aminocarbamate ayant au moins un atome d'azote de base et présentant une masse moléculaire moyenne comprise entre environ 1000 et environ 3000; (b) un détergent d'injection comprenant une amine d'hydrocarbyle à chaîne ramifiée ayant au moins un atome d'azote de base et présentant une masse moléculaire moyenne comprise entre environ 300 et environ 700, la fraction hydrocarbyle étant dérivée de polymères d'oléfines contenant 2 à 6 atomes de carbone; (c) un désémulsifiant de carburant homogène avec les autres composants de ladite composition d'additif de carburant; et (d) un fluide porteur naturel ou synthétique.
EP91905183A 1990-02-15 1991-02-12 Composition d'additif de carburant Expired - Lifetime EP0468043B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US479310 1974-06-14
US47931090A 1990-02-15 1990-02-15
PCT/US1991/000934 WO1991012303A1 (fr) 1990-02-15 1991-02-12 Composition d'additif de carburant

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EP0468043A1 true EP0468043A1 (fr) 1992-01-29
EP0468043A4 EP0468043A4 (en) 1992-03-11
EP0468043B1 EP0468043B1 (fr) 1994-04-06

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EP (1) EP0468043B1 (fr)
JP (1) JP2854973B2 (fr)
AT (1) ATE103965T1 (fr)
CA (1) CA2049954C (fr)
DE (1) DE69101603T2 (fr)
DK (1) DK0468043T3 (fr)
ES (1) ES2051591T3 (fr)
WO (1) WO1991012303A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5503644A (en) * 1991-09-23 1996-04-02 Shell Oil Company Gasoline composition for reducing intake valve deposits in port fuel injected engines
JP3378034B2 (ja) * 1991-09-23 2003-02-17 シエル・インターナシヨナル・リサーチ・マートスハツペイ・ベー・ヴエー ガソリン組成物
GB9318908D0 (en) * 1993-09-13 1993-10-27 Exxon Research Engineering Co Additive concentrate for use with gasolines
US5567211A (en) * 1995-08-03 1996-10-22 Texaco Inc. Motor fuel detergent additives
US6723141B1 (en) * 1999-11-04 2004-04-20 Shell Oil Company Additive concentration
NZ535013A (en) 2002-03-14 2005-03-24 Shell Int Research Use of hydrocarbyl primary monoamines as gasoline additives

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3898056A (en) * 1972-12-26 1975-08-05 Chevron Res Hydrocarbylamine additives for distillate fuels
US3960515A (en) * 1973-10-11 1976-06-01 Chevron Research Company Hydrocarbyl amine additives for distillate fuels
US4191537A (en) * 1976-06-21 1980-03-04 Chevron Research Company Fuel compositions of poly(oxyalkylene) aminocarbamate
US4288612A (en) * 1976-06-21 1981-09-08 Chevron Research Company Deposit control additives
US4247301A (en) * 1978-06-19 1981-01-27 Chevron Research Company Deposit control and dispersant additives
US4197409A (en) * 1978-08-08 1980-04-08 Chevron Research Company Poly(oxyalkylene)aminocarbomates of alkylene polyamine
US4274837A (en) * 1978-08-08 1981-06-23 Chevron Research Company Deposit control additives and fuel compositions containing them
US4270930A (en) * 1979-12-21 1981-06-02 Chevron Research Company Clean combustion chamber fuel composition
US4810263A (en) * 1986-04-11 1989-03-07 Exxon Research And Engineering Company Fuel composition
US4877416A (en) * 1987-11-18 1989-10-31 Chevron Research Company Synergistic fuel compositions

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9112303A1 *

Also Published As

Publication number Publication date
EP0468043B1 (fr) 1994-04-06
CA2049954C (fr) 2003-04-01
JP2854973B2 (ja) 1999-02-10
DE69101603D1 (de) 1994-05-11
DK0468043T3 (da) 1994-05-02
EP0468043A4 (en) 1992-03-11
ES2051591T3 (es) 1994-06-16
WO1991012303A1 (fr) 1991-08-22
JPH04506681A (ja) 1992-11-19
ATE103965T1 (de) 1994-04-15
CA2049954A1 (fr) 1991-08-16
DE69101603T2 (de) 1994-07-21

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