EP2169034A2 - Compositions de carburant - Google Patents

Compositions de carburant Download PDF

Info

Publication number
EP2169034A2
EP2169034A2 EP09252359A EP09252359A EP2169034A2 EP 2169034 A2 EP2169034 A2 EP 2169034A2 EP 09252359 A EP09252359 A EP 09252359A EP 09252359 A EP09252359 A EP 09252359A EP 2169034 A2 EP2169034 A2 EP 2169034A2
Authority
EP
European Patent Office
Prior art keywords
fuel composition
fuel
ppm
composition
antioxidant
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
EP09252359A
Other languages
German (de)
English (en)
Other versions
EP2169034B1 (fr
EP2169034A3 (fr
Inventor
David John Claydon
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.)
Afton Chemical Corp
Original Assignee
Afton Chemical Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Afton Chemical Corp filed Critical Afton Chemical Corp
Priority to EP09252359.6A priority Critical patent/EP2169034B1/fr
Publication of EP2169034A2 publication Critical patent/EP2169034A2/fr
Publication of EP2169034A3 publication Critical patent/EP2169034A3/fr
Application granted granted Critical
Publication of EP2169034B1 publication Critical patent/EP2169034B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
  • a fuel composition comprising (a) a major amount of a middle distillate fuel comprising from about 0.5% to about 30% by weight fatty acid methyl esters, relative to the total amount of the fuel composition; and (b) a minor amount 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 said fuel composition demonstrates reduced sediment formation as compared to a fuel composition devoid of the additive composition.
  • a method of reducing sediment formation in a fuel composition comprising providing a major amount of a middle distillate fuel comprising from about 0.5% to about 30% by weight fatty acid methyl esters; and mixing with said fuel a minor amount 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 ash less dispersant.
  • an ashless dispersant to reduce sediment formation in a fuel composition comprising a major amount of a middle distillate fuel comprising from about 0.5% to about 30% by weight fatty acid methyl esters, relative to the total amount of the fuel composition.
  • the use of the ashless dispersant can thus reduce sediment formation compared with a fuel which does not contain the ashless dispersant.
  • the invention also provides the use 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 to reduce sediment formation in a fuel composition.
  • the fuel composition comprises a major amount of a middle distillate fuel comprising from about 0.5% to about 30% by weight fatty acid methyl esters, relative to the total amount of the fuel composition.
  • This antioxidant system 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 of a middle distillate fuel comprising from about 0.5% to about 30% by weight fatty acid methyl esters, relative to the total amount of the fuel composition; and (b) a minor amount of an additive composition comprising an antioxidant system comprising at least one aromatic amine antioxidant and at least one phenolic antioxidant, and at least one ash less dispersant, wherein said fuel composition demonstrates reduced sediment formation as compared to a fuel composition devoid of the additive composition.
  • 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 up 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 about 80 to about 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.
  • 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 disclosures of which are incorporated herein in their entirety.
  • 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 about 180° to about 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 about 500 to about 5,000, for example from about 900 to about 2,000, for instance from about 900 to about 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 about 1
  • 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 about 500 to about 5,000, such as from about 900 to about 2,000, for example from about 900 to about 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 about 20 to about 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 about 10 to about 60 isobutylene groups, such as from about 20 to about 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 about 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 about 60%, such about 70% to about 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 about 0.8 to about 1 succinic anhydride group per hydrocarbyl substituent.
  • the weight ratio of succinic anhydride groups to alkylene groups can range from about 0.5 to about 3.5, such as from about 1 to about 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 about 1:1 to about 1 :2.5, such as from about 1:1 to about 1 :2.2.
  • Suitable reaction temperatures can range from about 155°C to about 200°C, such as from about 160°C to about 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 about 1 hour to about 8 hours, for example, within the range of about 2 hours to about 6 hours.
  • the ashless dispersant can be present in the disclosed fuel composition in any desired or effective amount, such as a sediment reducing amount.
  • the ashless dispersant such as a hydrocarbyl-substituted succinimide
  • the disclosed fuel compositions can include an antioxidant system.
  • Such antioxidants are well known and there is no particular restriction of the type of antioxidant employed, provided it is oil-soluble or oil-dispersible.
  • Suitable antioxidants include, but are not limited to, amininic antioxidants, aromatic antioxidants, cyclic amine antioxidants, and aromatic amine antioxidants, such as alkyl substituted diphenylamine, alkyl substituted phenyl, and napthylamines.
  • Suitable aromatic antioxidants include, but are not limited to, hindered phenols, mixed methylene bridged polyalkyl phenols, and the like.
  • Suitable hindered phenols include 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).
  • Suitable aromatic amine antioxidants include, but are not limited to, diphenylamine, alkyldiphenylamines having one or more alkyl substituents each comprising up to about 16 carbon atoms, phenyl-alpha-naphthyl amine, phenyl-beta- naphthylamine, alkyl-substituted phenyl-alpha-naphthylamine or phenyl-beta- naphthylamine having one or more alkyl substituents each comprising up to about 16 carbon atoms, and the like.
  • Non-limiting examples of suitable alkyl substituents include t-butyl, t-pentyl, hexyl, n-octyl, t-octyl, nonyl, decyl and dodecyl.
  • a non-limiting example of a cyclic amine antioxidant is N,N-dimethyl cyclohexamine.
  • the antioxidant system can be present in the fuel composition in any desired or effective amount, such as a sediment reducing amount.
  • the antioxidant system can be present in the fuel composition in an amount to provide from about 20 ppm to about 100 ppm, such as from about 20 ppm to about 80 ppm, for example from about 20 ppm to about 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 about 30%, such as from about 0.5% to about 30%, for example from about 10% to about 20% by weight relative to the total weight of the fuel composition, of fuel derived from biological sources.
  • the middle distillate fuel can comprise up to about 30% by weight of fatty acid methyl esters, such as from about 0.5% to about 30%, for example from about 10% to about 20% by weight of fatty acid methyl esters, relative to the total weight of the fuel composition.
  • the middle distillate fuel can be present in a major amount 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 of a middle distillate fuel comprising from about 0.5% to about 30% by weight fatty acid methyl esters; and mixing with said fuel a minor amount 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.

Landscapes

  • 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)
  • Liquid Carbonaceous Fuels (AREA)
EP09252359.6A 2009-10-05 2009-10-05 Compositions de carburant Active EP2169034B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP09252359.6A EP2169034B1 (fr) 2009-10-05 2009-10-05 Compositions de carburant

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP09252359.6A EP2169034B1 (fr) 2009-10-05 2009-10-05 Compositions de carburant

Publications (3)

Publication Number Publication Date
EP2169034A2 true EP2169034A2 (fr) 2010-03-31
EP2169034A3 EP2169034A3 (fr) 2010-04-14
EP2169034B1 EP2169034B1 (fr) 2017-05-17

Family

ID=41693017

Family Applications (1)

Application Number Title Priority Date Filing Date
EP09252359.6A Active EP2169034B1 (fr) 2009-10-05 2009-10-05 Compositions de carburant

Country Status (1)

Country Link
EP (1) EP2169034B1 (fr)

Cited By (1)

* 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

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3172892A (en) 1959-03-30 1965-03-09 Reaction product of high molecular weight succinic acids and succinic anhydrides with an ethylene poly- amine
US3202678A (en) 1959-08-24 1965-08-24 California Research Corp Alkenyl succinimides of tetraethylene pentamine
US3216936A (en) 1964-03-02 1965-11-09 Lubrizol Corp Process of preparing lubricant additives
US3254025A (en) 1961-08-18 1966-05-31 Lubrizol Corp Boron-containing acylated amine and lubricating compositions containing the same
US3272746A (en) 1965-11-22 1966-09-13 Lubrizol Corp Lubricating composition containing an acylated nitrogen compound
US4152499A (en) 1977-01-22 1979-05-01 Basf Aktiengesellschaft Polyisobutenes
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

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2156848A (en) * 1984-03-15 1985-10-16 Exxon Research Engineering Co Fuel additive
EP0203692B1 (fr) * 1985-04-26 1989-12-20 Exxon Chemical Patents Inc. Compositions d'huile combustible
AU668151B2 (en) * 1992-05-06 1996-04-26 Afton Chemical Corporation Composition for control of induction system deposits
JP2004531623A (ja) * 2001-02-14 2004-10-14 ザ　ルブリゾル　コーポレイション 燃料添加剤組成物および燃料組成物およびそれらの方法
GB0714725D0 (en) * 2007-07-28 2007-09-05 Innospec Ltd Fuel oil compositions and additives therefor

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3172892A (en) 1959-03-30 1965-03-09 Reaction product of high molecular weight succinic acids and succinic anhydrides with an ethylene poly- amine
US3219666A (en) 1959-03-30 1965-11-23 Derivatives of succinic acids and nitrogen compounds
US3202678A (en) 1959-08-24 1965-08-24 California Research Corp Alkenyl succinimides of tetraethylene pentamine
US3254025A (en) 1961-08-18 1966-05-31 Lubrizol Corp Boron-containing acylated amine and lubricating compositions containing the same
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
US4152499A (en) 1977-01-22 1979-05-01 Basf Aktiengesellschaft Polyisobutenes
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

Cited By (1)

* 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

Also Published As

Publication number Publication date
EP2169034B1 (fr) 2017-05-17
EP2169034A3 (fr) 2010-04-14

Similar Documents

Publication Publication Date Title
AU2016203885B2 (en) Quaternary ammonium amide and/or ester salts
EP3127992B1 (fr) Additifs pour carburants permettant de réduire l'arrachement de métal
US7901471B2 (en) Fuel composition containing a medium substantially free of sulphur and process thereof
CA2694445C (fr) Compositions de fioul et additifs pour ces dernieres
RU2595527C2 (ru) Присадка к топливу для усовершенствованных эксплуатационных характеристик двигателей с впрыскиваемым топливом
US8709108B2 (en) Fuel compositions
AU2008303345B2 (en) Fuel compositions
US20120103290A1 (en) Synergistic Combination of a Hindered Phenol and Nitrogen Containing Detergent for Biodiesel Fuel to Improve Oxidative Stability
EP2910625A1 (fr) Additif de carburant pour une performance améliorée dans des moteurs à injection
GB2488633A (en) Fuel additives to maintain optimum injector performance
EP3091063A1 (fr) Additif de carburant pour une meilleure performance d'injecteur
KR101435270B1 (ko) 저황 디젤 연료의 개선된 성능을 위한 연료 첨가제
RU2695347C2 (ru) Способы и применения для борьбы с отложениями на клапанах в двигателях с искровым зажиганием с прямым впрыскиванием топлива
KR20120016153A (ko) 효율의 개선 방법
EP2910626B1 (fr) Additif de carburant pour moteurs diesel
US20070245620A1 (en) Diesel fuel compositions
KR20080009753A (ko) 기관 흡입밸브 점착을 제거하는 방법으로서 지방산알콕실레이트의 용도
EP2169034B1 (fr) Compositions de carburant
AU2013201711B2 (en) Fuel additives for treating internal deposits of fuel injectors
AU2013202013B2 (en) Fuel compositions
WO2014184066A1 (fr) Polyalcénylsuccinimides pour réduire l'encrassement d'injecteurs dans des moteurs à allumage commandé et injection directe
KR20230030541A (ko) 만니히 기반 4차 암모늄염 연료 첨가제
KR20230030548A (ko) 만니히 기반 4차 암모늄염 연료 첨가제

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR

AX Request for extension of the european patent

Extension state: AL BA RS

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR

AX Request for extension of the european patent

Extension state: AL BA RS

17P Request for examination filed

Effective date: 20100727

17Q First examination report despatched

Effective date: 20100824

RBV Designated contracting states (corrected)

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR

REG Reference to a national code

Ref country code: DE

Ref legal event code: R079

Ref document number: 602009046111

Country of ref document: DE

Free format text: PREVIOUS MAIN CLASS: C10L0001140000

Ipc: C10L0001183000

RIC1 Information provided on ipc code assigned before grant

Ipc: C10L 1/183 20060101AFI20161010BHEP

Ipc: C10L 1/2383 20060101ALI20161010BHEP

Ipc: C10L 1/14 20060101ALI20161010BHEP

Ipc: C10L 10/04 20060101ALI20161010BHEP

Ipc: C10L 10/00 20060101ALI20161010BHEP

Ipc: C10L 1/223 20060101ALI20161010BHEP

Ipc: C10L 1/222 20060101ALI20161010BHEP

Ipc: C10L 10/18 20060101ALI20161010BHEP

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20161207

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 894476

Country of ref document: AT

Kind code of ref document: T

Effective date: 20170615

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602009046111

Country of ref document: DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20170517

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 894476

Country of ref document: AT

Kind code of ref document: T

Effective date: 20170517

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 9

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170517

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170517

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170517

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170517

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170517

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170817

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170818

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170817

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170517

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170917

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170517

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170517

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170517

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170517

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170517

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170517

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170517

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170517

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602009046111

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170517

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170517

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20180220

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170517

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170517

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20171005

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20171031

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20171031

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20171005

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 10

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20171005

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20091005

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170517

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170517

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170517

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170517

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20231025

Year of fee payment: 15

Ref country code: DE

Payment date: 20231027

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20231027

Year of fee payment: 15