EP0468043B1 - Treibstoffadditivzusammensetzung - Google Patents

Treibstoffadditivzusammensetzung Download PDF

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Publication number
EP0468043B1
EP0468043B1 EP91905183A EP91905183A EP0468043B1 EP 0468043 B1 EP0468043 B1 EP 0468043B1 EP 91905183 A EP91905183 A EP 91905183A EP 91905183 A EP91905183 A EP 91905183A EP 0468043 B1 EP0468043 B1 EP 0468043B1
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Prior art keywords
fuel
component
hydrocarbyl
amine
process according
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French (fr)
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EP0468043A4 (en
EP0468043A1 (de
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Thomas F. Buckley, Iii
David A. Kohler
Ralph E. Olsen
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Chevron USA Inc
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Chevron Research and Technology Co
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    • 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • 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 combustion 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 mile 3107.5- 9322.5 Km 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 aromatics, 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 and 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.
  • 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 additive 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 additive 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.
  • 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.
  • 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 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.
  • hydrocarbyl amines and hydrocarbyl polyamines as fuel additives is disclosed in U.S. Patent Nos.: 3,438,757; 3,898,056; and 3,565,804; 3,960,515 3,574,576
  • 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 molecular weight hydrocarbyl 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:
  • 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 65.6-204.4°C 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 complete 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 detergents, 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 combinations, provide complete gasoline intake system deposit control.
  • the instant invention demonstrates a new formulating 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.
  • novel fuel additive composition of the present invention is a homogeneous mixture which comprises the following components:
  • 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 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 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 C2 to C6 olefins.
  • the branched-chain hydrocarbyl group will ordinarily be prepared by polymerizing 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 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 polyisobutylene.
  • 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.
  • 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 alkylenediamine.
  • 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 pentamine.
  • 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 preparations 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 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 characteristics. These agents are typically selected from, but are not restricted to, alkylphenol resins, polyoxyalkylene-based fluids, alkylarylsulfonates, derivatives of fatty acids, and the like.
  • 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.
  • the fuel additive composition 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 demulsification of such emulsions and thereby help to clarify otherwise cloudy wet fuels. It is important to note that demulsifiers, when used in concentrations higher than about 25 ppm, can also promote emulsification.
  • 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.
  • concentration 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 65.5 to 204.4°C.
  • 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., dichlorobenzene or alkyl halides, e.g., ethylene dibromide.
  • 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 hereinbelow 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 C30 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 mm2/s 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 alkylphenolformaldehyde 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 45.5°C a pour point, ASTM D-97, of 5°F (-15°C), and a viscosity of 263 SUS at 60°F (57.3 mm2/s @ 15.5°C).
  • the fuel additive composition of this invention exemplified by Sample 6A below, met the requirement of a rating of one, on both these tests.
  • 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.
  • Chevron Solvent 25 which is a mixture of C-9 blending aromatics available from Chevron U.S.A. Inc., San Francisco, California
  • Sample 6A contained Tolad® T-326 (as described in Ex. 4) as the demulsifier.
  • Sample 6B contained L-1562 as the demulsifier.
  • L-1562 is a commercially available demulsifier purchased from Petrolite Corporation, St. Louis, MO.
  • a third additive composition, Sample 6C, contained oleyl amine as the injector detergent, and is shown for comparison purposes.
  • Oleyl amine is a low molecular weight straight chain C18 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 without 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 (-17.7°C) 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 containing oleyl amine as an injector detergent, was centrifuged after cooling to 0°F (-17.7°C) 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.%.
  • the gasolines were tested for intake valve keep-clean effectiveness using a procedure which utilizes a 1981 Pontiac 2.5-liter engine mounted upon an engine test stand, and run for 90 hrs. This test simulates a type of severe field test service characterized by light load driving conditions.
  • the effectiveness of an additive package is determined by averaging the weights of accumulated intake valve deposits obtained by the end of test, and comparing these results with those obtained using identical test conditions and the unadditized fuel.
  • a good fuel additive package capable of complete intake system keep-clean performance will typically reduce base gasoline intake valve deposits.
  • This procedure utilizes a 1975 Toyota 2.2-liter engine mounted on an engine stand and equipped with a control system to carefully regulate test conditions and engine operating cycles.
  • the engine is first run for fifteen hours on a relatively clean-burning, additive-free alkylate fuel.
  • the octane requirement is determined, and the fuel is switched to a mixture of 70% unleaded regular gasoline and 30% of FCC Heavy gasoline.
  • the FCC Heavy component is employed to increase the rate of combustion chamber deposit accumulation during this phase of the test.
  • the final octane requirement measurement is made.
  • the fuel additive package of this invention contributed one half of one octane number more than the octane requirement observed for the unadditized fuel (Test 9A). This increase was significantly less than that observed for a commercial gasoline additive package consisting of a heavy polybutene amine made from a polybutene containing, on average, 100 carbons per molecule, and having an average molecular weight of about 1450, which is reacted stepwise with chlorine and ethylene diamine, and a large dose of carrier oil (Test 9B).

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

Claims (16)

  1. Verfahren zur Herstellung einer homogenen Treibstoffadditiv-Zusammensetzung, bei welchem Verfahren die folgenden Inhaltsstoffe vereinigt werden:
    (a) ein Dispergiermittel umfassend ein Hydrocarbyl-poly(oxyalkylen)aminocarbamat mit mindestens einem basischen Stickstoffatom und einem durchschnittlichen Molekulargewicht von etwa 1 000 bis etwa 3 000;
    (b) ein Injektor-Detergens umfassend ein verzweigtkettiges Hydrocarbylamin mit mindestens einem basischen Stickstoffatom und einem durchschnittlichen Molekulargewicht von etwa 300 bis etwa 700, worin der Hydrocarbyl-Teil von Polymeren aus C₂- bis C₆-Olefinen abgeleitet ist;
    (c) ein Treibstoff-Demulgator, welcher mit den anderen Komponenten der Treibstoffadditiv-Zusammensetzung homogen ist; und
    (d) ein natürliches oder synthetisches Trägerfluid.
  2. Verfahren nach Anspruch 1, worin die Hydrocarbylgruppe in Komponente (a) 1 bis etwa 30 Kohlenstoffatome enthält.
  3. Verfahren nach Anspruch 1 oder 2, worin die Hydrocarbylgruppe in Komponente (a) eine Alkylphenylgruppe ist.
  4. Verfähren nach Anspruch 3, worin der Alkyl-Teil in der Alkylphenylgruppe Tetrapropenyl ist.
  5. Verfahren nach irgendeinem vorhergehenden Anspruch, worin der Amin-Teil des Aminocarbamats von einem Polyamin mit 2 bis 12 Aminstickstoffatomen und 2 bis 40 Kohlenstoffatomen abgeleitet ist.
  6. Verfahren nach Anspruch 5, worin das Polyamin ein Polyalkylenpolyamin mit 2 bis 12 Aminstickstoffatomen und 2 bis 24 Kohlenstoffatomen ist.
  7. Verfahren nach Anspruch 6, worin das Polyalkylenpolyamin aus der Gruppe von Ethylendiamin, Propylendiamin, Diethylentriamin und Dipropylentriamin gewählt ist.
  8. Verfahren nach irgendeinem vorhergehenden Anspruch, worin der Poly(oxyalkylen)-Teil von Komponente (a) von C₂- bis C₅-Oxyalkyleneinheiten abgeleitet ist.
  9. Verfahren nach irgendeinem vorhergehenden Anspruch, worin das Hydrocarbyl-poly(oxyalkylen)aminocarbamat von Komponente (a) ein Alkylphenyl-poly(oxybutylen)aminocarbamat ist, worin der Amin-Teil von Ethylendiamin oder Diethylentriamin abgeleitet ist.
  10. Verfahren nach irgendeinem vorhergehenden Anspruch, worin der verzweigtkettige Hydrocarbyl-Teil von Komponente (b) Polypropenyl oder Polyisobutenyl ist.
  11. Verfahren nach irgendeinem vorhergehenden Anspruch, worin die Aminogruppe des verzweigtkettigen Hydrocarbylamins von Komponente (b) aus der Gruppe von Ethylendiamin, Diethylentriamin, Triethylentetramin und Tetraethylenpentamin gewählt ist.
  12. Verfahren nach irgendeinem vorhergehenden Anspruch, worin das verzweigtkettige Hydrocarbylamin von Komponente (b) ein Polyisobutenylethylendimin ist.
  13. Verfahren nach Anspruch 1, worin die Komponente (a) ein Alkylphenyl-poly(oxybutylen)aminocarbamat ist, worin der Amin-Teil von Ethylendiamin oder Diethylentriamin abgeleitet ist, und Komponente (b) ein Polyisobutenylethylendiamin ist.
  14. Verfahren zur Herstellung einer Treibstoff-Zusammensetzung, bei welchem Verfahren ein Kohlenwasserstoff, der im Benzin- oder Dieselbereich siedet, und etwa 400 bis etwa 1 200 Teile pro Million homogene Treibstoffadditiv-Zusammensetzung, hergestellt nach einem Verfahren, wie es in irgendeinem der Ansprüche 1 bis 13 beansprucht ist, vereinigt werden.
  15. Verfahren nach Anspruch 14, worin die erhaltene Treibstoff-Zusammensetzung enthält: etwa 100 bis 225 ppm Dispergiermittel von Komponente (a), etwa 10 bis 70 ppm Injektor-Detergens von Komponente (b), etwa 5 bis 25 ppm Demulgator von Komponente (c) und etwa 250 bis 800 ppm Trägerfluid von Komponente (d).
  16. Verfahren zur Herstellung eines Treibstoff-Konzentrates, bei welchem Verfahren ein inertes, stabiles, oleophiles organisches Lösungsmittel, welches im Bereich von 150° bis 400°F (65,6 bis 204,4°C) siedet, und mit etwa 5 bis 50 Gewichtsprozent homogene Treibstoffadditiv-Zusammensetzung, hergestellt nach einem Verfahren, wie es in irgendeinem der Ansprüche 1 bis 13 beansprucht ist, vereinigt werden.
EP91905183A 1990-02-15 1991-02-12 Treibstoffadditivzusammensetzung Expired - Lifetime EP0468043B1 (de)

Applications Claiming Priority (3)

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US47931090A 1990-02-15 1990-02-15
PCT/US1991/000934 WO1991012303A1 (en) 1990-02-15 1991-02-12 Fuel additive composition
US479310 2000-01-06

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

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JP (1) JP2854973B2 (de)
AT (1) ATE103965T1 (de)
CA (1) CA2049954C (de)
DE (1) DE69101603T2 (de)
DK (1) DK0468043T3 (de)
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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
ES2095392T3 (es) * 1991-09-23 1997-02-16 Shell Int Research Composicion de gasolina.
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
ES2268344T3 (es) 2002-03-14 2007-03-16 Shell Internationale Research Maatschappij B.V. Aditivos para gasolina.

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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

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DK0468043T3 (da) 1994-05-02
ATE103965T1 (de) 1994-04-15
DE69101603D1 (de) 1994-05-11
EP0468043A4 (en) 1992-03-11
CA2049954C (en) 2003-04-01
JP2854973B2 (ja) 1999-02-10
DE69101603T2 (de) 1994-07-21
EP0468043A1 (de) 1992-01-29
CA2049954A1 (en) 1991-08-16
ES2051591T3 (es) 1994-06-16
JPH04506681A (ja) 1992-11-19
WO1991012303A1 (en) 1991-08-22

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