EP2169034B1 - Compositions de carburant - Google Patents

Compositions de carburant Download PDF

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Publication number
EP2169034B1
EP2169034B1 EP09252359.6A EP09252359A EP2169034B1 EP 2169034 B1 EP2169034 B1 EP 2169034B1 EP 09252359 A EP09252359 A EP 09252359A EP 2169034 B1 EP2169034 B1 EP 2169034B1
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ppm
fuel
fuel composition
antioxidant
composition
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German (de)
English (en)
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EP2169034A3 (fr
EP2169034A2 (fr
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David John Claydon
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Afton Chemical Corp
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Afton Chemical Corp
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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, 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
    • 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
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/18—Use of additives to fuels or fires for particular purposes use of detergents or dispersants for purposes not provided for in groups C10L10/02 - C10L10/16
    • 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
    • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
    • C10L1/183—Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom
    • 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
    • C10L1/223—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond having at least one amino group bound to an aromatic carbon atom
    • 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)

Definitions

  • This disclosure relates generally to fuel compositions. More specifically, the present disclosure is directed to middle distillate fuel compositions, such as diesel and/or biodiesel fuel compositions, suitable for home heating applications and the like.
  • middle distillate fuels such as diesel fuel, including heating oil.
  • middle distillate fuel compositions often contained ash-producing metals, such as manganese or iron to obtain good soot reduction upon combustion.
  • ash-producing metals such as manganese or iron
  • the move to ashless technology is being driven by the introduction of highly efficient burner technology coupled with new boiler hardware that is based on a condenser design, whereby condensed water goes into the public water system.
  • metallic combustion improvers such as those based on iron or manganese
  • fuel compositions without ash-producing metals have not demonstrated completely acceptable performance.
  • the industry has recently experienced operational difficulties resulting from the production of insoluble sediment in middle distillate fuels, including heating oil.
  • middle distillate fuels particularly for home heating oils, such as biodiesel fuel, for example diesel fuels containing 10% fuel derived from biological sources (also known as “biodiesel 10" or “B10"), that effectively reduces sediment formation in fuel compositions and improves heating power in home heating applications.
  • biodiesel fuel for example diesel fuels containing 10% fuel derived from biological sources (also known as “biodiesel 10" or “B10")
  • B10 biological sources
  • WO2009016400 describes the use of a nitrogen-containing dispersant as an antioxidant additive in a fuel composition comprising biofuel.
  • a fuel composition comprising (a) a major amount (at least 50 weight percent) of a middle distillate fuel comprising from 0.5% to 30% by weight fatty acid methyl esters, relative to the total amount of the fuel composition; and (b) a minor amount (less than 50 weight percent) of an additive composition comprising an antioxidant system comprising at least one cyclic amine antioxidant and at least one phenolic antioxidant, and at least one ashless dispersant, wherein: the at least one ashless dispersant is a hydrocarbyl-substituted succinimide which is present in the fuel composition in an amount of 60 ppm to 300 ppm; and the cyclic amine antioxidant is N,N-dimethyl cyclohexamine; the phenolic antioxidant is a tertiary butyl phenol; and wherein in the fuel composition, the antioxidant system is present in an amount to deliver from 20 ppm to 100 ppm of the cyclic amine antioxidant and from 20 ppm to 100
  • Also disclosed is a method of reducing sediment formation in a fuel composition comprising providing a major amount (at least 50 weight percent) of a middle distillate fuel comprising from 0.5% to 30% by weight fatty acid methyl esters; and mixing with said fuel a minor amount (less than 50 weight percent) of an additive composition comprising an antioxidant system comprising at least one cyclic amine antioxidant and at least one phenolic antioxidant, and at least one ashless dispersant, wherein: the at least one ashless dispersant is a hydrocarbyl-substituted succinimide which is present in the fuel composition in an amount of 60 ppm to 300 ppm; the cyclic amine antioxidant is N,N-dimethyl cyclohexamine; and the phenolic antioxidant is a tertiary butyl phenol; and wherein in the fuel composition, the antioxidant system is used in an amount to deliver from 20 ppm to 100 ppm of the cyclic amine antioxidant and from 20 ppm to 100 ppm of the
  • an ashless dispersant as defined herein and an antioxidant system as defined herein to reduce sediment formation in a fuel composition comprising a major amount (at least 50 weight percent) of a middle distillate fuel comprising from 0.5% to 30% by weight fatty acid methyl esters, relative to the total amount of the fuel composition.
  • a middle distillate fuel comprising from 0.5% to 30% by weight fatty acid methyl esters
  • the invention also provides the use of an additive composition as defined above to reduce sediment formation in a fuel composition.
  • the fuel composition comprises a major amount (at least 50 weight percent) of a middle distillate fuel comprising from 0.5% to 30% by weight fatty acid methyl esters, relative to the total amount of the fuel composition.
  • the use of the antioxidant system and dispersant can thus reduce sediment formation compared with a fuel which does not contain the antioxidant system, and in particular compared with a fuel which does not contain the ashless dispersant.
  • the present disclosure relates to a fuel composition
  • a fuel composition comprising (a) a major amount (at least 50 weight percent) of a middle distillate fuel comprising from 0.5% to 30% by weight fatty acid methyl esters, relative to the total amount of the fuel composition; and (b) a minor amount (less than 50 weight percent) of an additive composition comprising an antioxidant system comprising at least one cyclic amine antioxidant and at least one phenolic antioxidant, and at least one ashless dispersant, wherein: the at least one ashless dispersant is a hydrocarbyl-substituted succinimide which is present in the fuel composition in an amount of 60 ppm to 300 ppm; the cyclic amine antioxidant is N,N-dimethyl cyclohexamine; and the phenolic antioxidant is a tertiary butyl phenol; and wherein in the fuel composition, the antioxidant system is present in an amount to deliver from 20 ppm to 100 ppm of the cyclic amine antioxidant and from 20
  • middle distillate fuel is understood to mean one or more fuels selected from the group consisting of diesel fuel, biodiesel, biodiesel-derived fuel, synthetic diesel, diesel fuel treated with oxygenates for particulate control, mixtures thereof, and other products meeting the definitions of ASTM 0975.
  • the middle distillate fuel can contain up to 30%, for example from about 0.5% to about 30%, such as from about 10% to about 20%, fuel derived from biological sources.
  • biodiesel is understood to mean diesel fuel comprising fuel derived from biological sources.
  • the middle distillate fuel can be derived from biological sources such as oleaginous seeds, for example rapeseed, sunflower, soybean seeds, and the like.
  • the seeds can be submitted to grinding and/or solvent extraction treatments (e.g., with n-hexane) in order to extract the oil, which comprises triglycerides of saturated and unsaturated (mono- and poly-unsaturated, in mixture with each other, in proportions depending on the selected oleaginous seed) C 16 -C 22 fatty acids.
  • the oil can be submitted to a filtration and refining process, in order to remove any possible free fats and phospholipids present, and can be submitted to a transesterification reaction with methanol in order to prepare the methyl esters of the fatty acids (fatty acid methyl esters, also known as "FAME").
  • fatty acid methyl esters also known as "FAME"
  • the middle distillate fuel comprises from about 10% to about 20% by weight fatty acid methyl esters
  • middle distillate fuel containing from 0.5% to 30% fatty acid methyl esters e.g., B10 or B20 fuel
  • the fuel tends to form sediment, which can contribute to pump failure prior to combustion. It is believed, without being limited by theory, that oxidation of fatty acid methyl esters can cause sediment formation, which can block pumps and cause pump failure.
  • the term “major amount” is understood to mean an amount greater than or equal to 50 wt.%, for example from 80 to 98 wt.% relative to the total weight of the composition.
  • the term “minor amount” is understood to mean an amount less than 50 wt.% relative to the total weight of the composition.
  • aromatic refers to the typical substituted or unsubstituted non-aliphatic hydrocarbyl or heterocyclic moieties of this class, e.g., a polyunsaturated, typically aromatic, hydrocarbyl cyclical, or heterocyclic, substituent, which can have a single ring or multiple rings (up to three rings) that are fused together or linked covalently.
  • Typical hydrocarbyl aromatic moieties include phenyl, naphthyl, biphenylenyl, phenanthrenyl, phenalenyl, and the like. Such moieties are optionally substituted with one or more hydrocarbyl substituents.
  • aryl moieties substituted by other aryl moieties such as biphenyl.
  • Heterocyclic aryl or aromatic moieties refers to unsaturated cyclical moieties containing carbon atoms in the ring and additionally one or more hetero atoms, which are typically oxygen, nitrogen, sulfur and/or phosphorus, such as pyridyl, thienyl, furyl, thiazolyl, pyranyl, pyrrolyl, pyrazolyl, imidazolyl, pyrazinyl, thiazolyl, etc.
  • Such moieties are optionally substituted with one or more substituents such as hydroxy, optionally substituted lower alkyl, optionally substituted lower alkoxy, amino, amide, ester moieties and carbonyl moieties (e.g., aldehyde or ketonic moieties).
  • substituents such as hydroxy, optionally substituted lower alkyl, optionally substituted lower alkoxy, amino, amide, ester moieties and carbonyl moieties (e.g., aldehyde or ketonic moieties).
  • hydrocarbyl group or “hydrocarbyl” is used in its ordinary sense, which is well-known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the remainder of a molecule and having a predominantly hydrocarbon character. Examples of hydrocarbyl groups include:
  • lower in terms of “lower alkyl” etc. refers to a group containing from 1 to 10, for example from 1 to 6, carbon atoms.
  • succinimide is meant to encompass the completed reaction product from reaction between an amine and a hydrocarbyl-substituted succinic acid or anhydride (or like succinic acylating agent), and is intended to encompass compounds wherein the product may have amide, and/or salt linkages in addition to the imide linkage of the type that results from the reaction of or contact with an amine and an anhydride moiety.
  • reacting herein with regard to the alkylation is meant the product or result of contacting, exposing or bringing together any of the recited components or chemicals, whether a covalent bond, ionic bond, salt or other association is produced.
  • Ashless dispersants are described in numerous patent specifications, mainly as additives for use in lubricant compositions, but their use in middle distillate fuels has also been described. Ashless dispersants leave little or no residue upon combustion. They generally contain only carbon, hydrogen, oxygen and in most cases nitrogen, but sometimes contain in addition other elements such as phosphorus, sulfur, or boron.
  • the ashless dispersants for use in the invention are hydrocarbyl-substituted succinimides.
  • the ashless dispersant compounds suitable for use in the fuel compositions of the present disclosure can be a hydrocarbyl-substituted succinimide of an amine having at least one primary amino group capable of forming an imide group. Representative examples are given in U.S. Pat. Nos. 3,172,892 ; 3,202,678 ; 3,216,936 ; 3,219,666 ; 3,254,025 ; 3,272,746 ; and 4,234,435 .
  • the hydrocarbyl-substituted succinimides can be formed by conventional methods such as by heating a hydrocarbyl-substituted succinic anhydride, acid, acid- ester, acid halide, or lower alkyl ester with an amine containing at least one primary amino group.
  • the hydrocarbyl-substituted succinic anhydride can be made readily by heating a mixture of olefin and maleic anhydride to 180° to 220°C.
  • the olefin can be a polymer or copolymer of a lower monoolefin such as ethylene, propylene, isobutene and the like.
  • the hydrocarbyl-substituent is derived from polyisobutene having a number average molecular weight, as determined by gel permeation chromatography, of up to 10,000 or higher, such as from 500 to 5,000, for example from 900 to 2,000, for instance from 900 to 1,200.
  • Amines that can be employed in forming the ashless dispersant include any that have at least one primary amino group which can react to form an imide group.
  • a few non-limiting representative examples include methylamine, 2-ethylhexylamine, n-dodecylamine, stearylamine, N,N-dimethyl-propanediamine, N-(3- aminopropyl)morpholine, N-dodecyl-propanediamine, N-aminopropyl-piperazine, ethanolamine, N-ethanol-ethylenediamine and the like.
  • the amines can be alkylene polyamines such as propylene diamine, dipropylene triamine, di-(1,2-butylene)triamine, and tetra-(1,2-propylene)pentamine.
  • the amines are the ethylene polyamines that can be depicted by the formula H 2 N(CH 2 CH 2 NH) n H, wherein n is an integer from one to about ten.
  • Non-limiting examples include: ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, and the like, including mixtures thereof (in which case n is the average value of the mixture.) These ethylene polyamines have a primary amine group at each end and so can form mono-alkenylsuccinimides and bis-alkenylsuccinimides. Commercially available ethylene polyamine mixtures usually contain minor amounts of branched species and cyclic species such as N-aminoethyl piperazine, N,N'-bis(aminoethyl)piperazine, N,N'-bis(piperazinyl)ethane, and like compounds. In another embodiment, commercial mixtures can have approximate overall compositions falling in the range corresponding to diethylene triamine to tetraethylene pentamine. In a further embodiment, commercial mixtures can generally correspond in overall makeup to tetraethylene pentamine.
  • useful ashless dispersants for use in the present invention can be the products of reaction of a polyethylene polyamine (e.g.triethylene tetramine or tetra ethylene pentamine) with a hydrocarbyl-substituted carboxylic acid or anhydride made by reaction of a polyolefin (such as polyisobutene) with an unsaturated polycarboxylic acid or anhydride, e.g., maleic acid, fumaric acid, malic acid, tartaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid, ethylmaleic anhydride, dimethylmaleic anhydride, ethylmaleic acid, dimethylmaleic acid, hexylmaleic acid, and the like, including mixtures of two or more such substances.
  • the reaction product can form an amide based on intermolecular condensation upon standing for long periods of time, such as 1 to
  • the ashless dispersant can be a compound according to the following formula: wherein R 2 is a hydrocarbyl group having a number average molecular weight ranging from 500 to 5,000, such as from 900 to 2,000, for example from 900 to 1,200, as measured by GPC. Unless indicated otherwise, molecular weights in the present specification are number average molecular weights.
  • the R 2 hydrocarbyl groups can comprise one or more polymer units chosen from linear or branched alkenyl units.
  • the alkenyl units can have from 20 to 200 carbon atoms.
  • the hydrocarbyl group can comprise one or more linear or branched polymer units chosen from ethylene radicals, propylene radicals, butylene radicals, pentene radicals, hexene radicals, octene radicals and decene radicals.
  • the R 2 hydrocarbyl group can be in the form of, for example, a homopolymer, copolymer or terpolymer.
  • the hydrocarbyl group is polyisobutylene.
  • the hydrocarbyl group can be a homopolymer of polyisobutylene comprising from 10 to 60 isobutylene groups, such as from 20 to 30 isobutylene groups.
  • the polyalkenyl compounds used to form the R 2 hydrocarbyl groups can be formed by any suitable methods, such as by conventional catalytic oligomerization of alkenes.
  • the R 2 hydrocarbyl group can be derived from a linear alpha olefin or an acid-isomerized alpha olefin made by the oligomerization of ethylene by methods well known in the art. These hydrocarbyl groups can range from 8 carbon atoms to over 40 carbon atoms.
  • hydrocarbyl groups of this type can be derived from a linear C 18 or a mixture of C 20 - 24 alpha olefins or from acid-isomerized C 16 alpha olefins.
  • polyisobutylenes having at least 60%, such 70% to 90% and above, terminal vinylidene content can be used to form the R2 hydrocarbyl group.
  • terminal vinylidene content is understood to mean terminal olefinic double bond content.
  • Such polymers are referred to as highly reactive polyisobutylenes (HR-PIB).
  • HR-PIB highly reactive polyisobutylenes
  • approximately one mole of maleic anhydride can be reacted per mole of polyolefin, such that the resulting polyalkenyl succinic anhydride has 0.8 to 1 succinic anhydride group per hydrocarbyl substituent.
  • the weight ratio of succinic anhydride groups to alkylene groups can range from 0.5 to 3.5, such as from 1 to 1.1.
  • the reactants described above can be mixed together under suitable conditions to provide the desired reaction products of the present disclosure.
  • the reactant compounds can be mixed together in a mole ratio of hydrocarbyl- substituted succinic acid or anhydride to amine ranging from 1:1 to 1 :2.5, such as from 1:1 to 1 :2.2.
  • Suitable reaction temperatures can range from 155°C to 200°C, such as from 160°C to 190°C.
  • Any suitable reaction pressures may be used, such as, atmospheric pressures, subatmospheric pressures or superatmospheric pressures. However, the range of temperatures can be different from those listed where the reaction is carried out at other than atmospheric pressure.
  • the reaction can be carried out for a period of time within the range of 1 hour to 8 hours, for example, within the range of 2 hours to 6 hours.
  • the hydrocarbyl-substituted succinimide ashless dispersant is present in the disclosed fuel composition in an amount of 60 ppm to 300 ppm, which is a sediment reducing amount.
  • the hydrocarbyl-substituted succinimide can be present in the fuel composition in an amount ranging for example from 60 ppm to 200 ppm, such as from 60 ppm to 90 ppm.
  • the disclosed fuel compositions include an antioxidant system comprising at least one cyclic amine antioxidant and at least one phenolic antioxidant.
  • Suitable phenolic antioxidants are tertiary butyl phenols, in particular di-substituted tertiary butyl phenols.
  • Suitable tertiary butyl phenols include 2,6-di-tert-butyl-phenol, 2,4,6-tri-tert-butyl-phenol, 4-methyl-2,6-di-tert-butyl-phenol, 2,4-dimethyl-6-tert-butyl-phenol and 4,4'-methylenebis(2,6-di-tert-butyl-phenol).
  • the cyclic amine antioxidant is N,N-dimethyl cyclohexamine.
  • the antioxidant system is present in the fuel composition in an amount to deliver from 20 ppm to 100 ppm of the cyclic amine antioxidant and from 20 ppm to 100 ppm of the phenolic antioxidant, which is a sediment reducing amount.
  • the antioxidant system can be present in the fuel composition in an amount to provide from 20 ppm to 80 ppm, for example from 20 ppm to 40 ppm, of the antioxidants to the fuel composition.
  • Middle distillate fuels for use in the disclosed composition include, but are not limited to, home heating oils.
  • the present disclosure is thus applicable to such fuels as kerosene, jet fuel, aviation fuel, diesel fuel, light cycle oil, heavy cycle oil, light gas oil, heavy gas oil, bunker fuels, residual fuel oils, ultra heavy fuel oils, and in general, any liquid (or flowable) hydrocarbonaceous product suitable for combustion either in an engine (e.g., diesel fuel, gas turbine fuels, etc.) or in a burner apparatus (e.g., gas oils, inland heavy fuel oil, residual fuel oils, visbreaker fuel oils, home heating oils, etc.).
  • an engine e.g., diesel fuel, gas turbine fuels, etc.
  • a burner apparatus e.g., gas oils, inland heavy fuel oil, residual fuel oils, visbreaker fuel oils, home heating oils, etc.
  • suitable fuels can include liquid fuels derived from biological sources, such as vegetable oils (e.g., rapeseed oil, jojoba oil, cottonseed oil, etc.); or refuse- derived liquid fuels such as fuels derived from municipal and/or industrial wastes; or waste oils and/or liquid waste biomass and its derivatives; or mixtures of any of the foregoing substances.
  • vegetable oils e.g., rapeseed oil, jojoba oil, cottonseed oil, etc.
  • refuse- derived liquid fuels such as fuels derived from municipal and/or industrial wastes; or waste oils and/or liquid waste biomass and its derivatives; or mixtures of any of the foregoing substances.
  • the middle distillate fuel comprises up to 30%, such as from 0.5% to 30%, for example from 10% to 20% by weight relative to the total weight of the fuel composition, of fuel derived from biological sources.
  • the middle distillate fuel comprises from 0.5% to 30%, for example from 10% to 20% by weight of fatty acid methyl esters, relative to the total weight of the fuel composition.
  • the middle distillate fuel is present in a major amount (at least 50 weight percent) in the fuel composition.
  • the fuel compositions of the present disclosure can contain other additives.
  • additives include supplementary dispersants/detergents, antioxidants, thermal stabilizers, carrier fluids, metal deactivators, dyes, markers, corrosion inhibitors, biocides, antistatic additives, drag reducing agents, friction modifiers, demulsifiers, emulsifiers, dehazers, anti-icing additives, antiknock additives, anti-valve-seat recession additives, surfactants, other lubricity additives combustion improvers, cetane number improvers, and mixtures thereof.
  • a diesel fuel comprising 10% fatty acid methyl esters was formulated with different combinations of dispersants and antioxidants according to Table 1 above.
  • HiTEC® 4036 delivered 38 ppm 2,6-di-tert-butylphenol, 20 ppm N,N-dimethyl cyclohexamine, and 30 ppm succinimide to the finished fuel.
  • the fuel samples were stored at 50°C for 3 months. At the end of 3 months, a visible examination of sediment formation was conducted.
  • samples 1 through 8 delivered increasing amounts of different phenolic antioxidants in an attempt to prevent sediment formation. However, all of samples 1 through 8 formed sediment. Thus, it is evident from the results above that increasing the amount of antioxidant does not reduce sediment formation.
  • a method of reducing sediment formation in a fuel composition comprising: providing a major amount (at least 50 weight percent) of a middle distillate fuel comprising from 0.5% to 30% by weight fatty acid methyl esters; and mixing with said fuel a minor amount (less than 50 weight percent) of an additive composition comprising an antioxidant system comprising at least one cyclic amine antioxidant and at least one phenolic antioxidant, and at least one ashless dispersant, wherein: the at least one ashless dispersant is a hydrocarbyl-substituted succinimide which is present in the fuel composition in an amount of 60 ppm to 300 ppm; the cyclic amine antioxidant is N,N-dimethyl cyclohexamine; and the phenolic antioxidant is a tertiary butyl phenol; and wherein in the fuel composition, the antioxidant system is present in an amount to deliver from 20 ppm to 100 ppm of the cyclic amine antioxidant and from 20

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  • Organic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Liquid Carbonaceous Fuels (AREA)

Claims (8)

  1. Composition de combustible comprenant :
    (a) au moins 50 pour cent en poids d'un combustible de distillat moyen comprenant de 0,5 à 30 % en poids d'esters méthyliques d'acides gras, par rapport à la quantité totale de composition de combustible, et
    (b) moins de 50 pour cent en poids d'une composition d'additifs comprenant un système antioxydant comprenant au moins un antioxydant de type amine cyclique et au moins un antioxydant phénolique, et au moins un dispersant sans cendre ;
    dans laquelle
    - l'au moins un dispersant sans cendre est un succinimide à substitution hydrocarbyle qui est présent dans la composition de combustible en une quantité comprise entre 60 ppm et 300 ppm,
    - l'antioxydant de type amine cyclique est la N,N-diméthyl-cyclohexamine, et
    - l'antioxydant phénolique est un butylphénol tertiaire ;
    ladite composition de combustible comprenant le système antioxydant en une quantité permettant de fournir de 20 ppm à 100 ppm dudit antioxydant de type amine cyclique et de 20 ppm à 100 ppm dudit antioxydant phénolique.
  2. Composition de combustible selon la revendication 1, dans laquelle le substituant hydrocarbyle du succinimide est dérivé du polyisobutène d'un poids moléculaire moyen en nombre allant de 500 à 5000.
  3. Composition de combustible selon la revendication 1 ou 2, dans laquelle le succinimide à substitution hydrocarbyle est présent en une quantité allant de 60 ppm à 200 ppm, de préférence de 60 ppm à 90 ppm.
  4. Composition de combustible selon l'une quelconque des revendications précédentes, dans laquelle l'antioxydant phénolique est un butylphénol tertiaire disubstitué.
  5. Composition de combustible selon l'une quelconque des revendications précédentes, dans laquelle le combustible de distillat moyen comprend de 10 à 20 % en poids d'esters méthyliques d'acides gras.
  6. Composition de combustible selon l'une quelconque des revendications précédentes, comprenant en outre au moins un additif choisi dans le groupe constitué par des dispersants/détergents supplémentaires, antioxydants, stabilisants thermiques, fluides porteurs, désactivateurs de métaux, colorants, marqueurs, inhibiteurs de corrosion, biocides, additifs antistatiques, agents réduisant la résistance au frottement, modificateurs de frottement, désémulsifiants, émulsifiants, additifs antihumidité, additifs antigel, additifs anticliquetis, additifs anti-récession des sièges de soupape, tensioactifs, autres additifs lubrifiants, substances améliorant la combustion, améliorateurs de l'indice de cétane et mélanges de ceux-ci.
  7. Utilisation d'un dispersant sans cendre selon la revendication 1 ou 2 et d'un système antioxydant selon la revendication 1 ou 4, destinée à réduire la formation de sédiments dans une composition de combustible comprenant au moins 50 pour cent en poids d'un combustible de distillat moyen comprenant de 0,5 à 30 % en poids d'esters méthyliques d'acides gras par rapport à la quantité totale de la composition de combustible.
  8. Utilisation d'une composition d'additifs selon l'une quelconque des revendications 1 à 4, destinée à réduire la formation de sédiments dans une composition de combustible comprenant au moins 50 pour cent en poids d'un combustible de distillat moyen comprenant de 0,5 à 30 % en poids d'esters méthyliques d'acides gras, par rapport à la quantité totale de la composition de combustible.
EP09252359.6A 2009-10-05 2009-10-05 Compositions de carburant Active EP2169034B1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102559304A (zh) * 2011-12-31 2012-07-11 临沂实能德环保燃料化工有限责任公司 多功能车用生物柴油复合添加剂及其制备方法

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1248643B (de) 1959-03-30 1967-08-31 The Lubrizol Corporation, Cleveland, Ohio (V. St. A.) Verfahren zur Herstellung von öllöslichen aeylierten Aminen
NL124842C (fr) 1959-08-24
US3087936A (en) 1961-08-18 1963-04-30 Lubrizol Corp Reaction product of an aliphatic olefinpolymer-succinic acid producing compound with an amine and reacting the resulting product with a boron compound
US3216936A (en) 1964-03-02 1965-11-09 Lubrizol Corp Process of preparing lubricant additives
US3272746A (en) 1965-11-22 1966-09-13 Lubrizol Corp Lubricating composition containing an acylated nitrogen compound
DE2702604C2 (de) 1977-01-22 1984-08-30 Basf Ag, 6700 Ludwigshafen Polyisobutene
US4234435A (en) 1979-02-23 1980-11-18 The Lubrizol Corporation Novel carboxylic acid acylating agents, derivatives thereof, concentrate and lubricant compositions containing the same, and processes for their preparation
GB2156848A (en) * 1984-03-15 1985-10-16 Exxon Research Engineering Co Fuel additive
DE3667668D1 (de) * 1985-04-26 1990-01-25 Exxon Chemical Patents Inc Heizoelzusammensetzungen.
AU668151B2 (en) * 1992-05-06 1996-04-26 Afton Chemical Corporation Composition for control of induction system deposits
WO2002102942A2 (fr) * 2001-02-14 2002-12-27 The Lubrizol Corporation Composition d'additifs pour carburants, composition de carburants et procede associe
GB0714725D0 (en) * 2007-07-28 2007-09-05 Innospec Ltd Fuel oil compositions and additives therefor

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EP2169034A2 (fr) 2010-03-31

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