EP3330344B1 - Carburant d'aviation contenant des composés aromatiques ramifiés comprenant un rehausseur d'octane de manganèse - Google Patents

Carburant d'aviation contenant des composés aromatiques ramifiés comprenant un rehausseur d'octane de manganèse Download PDF

Info

Publication number
EP3330344B1
EP3330344B1 EP17204818.3A EP17204818A EP3330344B1 EP 3330344 B1 EP3330344 B1 EP 3330344B1 EP 17204818 A EP17204818 A EP 17204818A EP 3330344 B1 EP3330344 B1 EP 3330344B1
Authority
EP
European Patent Office
Prior art keywords
aviation gasoline
aromatic
volume percent
manganese
aviation
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.)
Active
Application number
EP17204818.3A
Other languages
German (de)
English (en)
Other versions
EP3330344A1 (fr
Inventor
Zachary John Mcafee
Joseph Anthony Calderone III
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
Publication of EP3330344A1 publication Critical patent/EP3330344A1/fr
Application granted granted Critical
Publication of EP3330344B1 publication Critical patent/EP3330344B1/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
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic 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
    • C10L1/30—Organic compounds compounds not mentioned before (complexes)
    • C10L1/305—Organic compounds compounds not mentioned before (complexes) organo-metallic compounds (containing a metal to carbon bond)
    • 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
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • 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
    • C10L1/103—Liquid carbonaceous fuels containing additives stabilisation of anti-knock agents
    • 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
    • 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
    • C10L10/10—Use of additives to fuels or fires for particular purposes for improving the octane number
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2200/00—Components of fuel compositions
    • C10L2200/02—Inorganic or organic compounds containing atoms other than C, H or O, e.g. organic compounds containing heteroatoms or metal organic complexes
    • C10L2200/0204—Metals or alloys
    • C10L2200/0236—Group VII metals: Mn, To, Re
    • 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
    • C10L2200/00—Components of fuel compositions
    • C10L2200/02—Inorganic or organic compounds containing atoms other than C, H or O, e.g. organic compounds containing heteroatoms or metal organic complexes
    • C10L2200/0254—Oxygen containing 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
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
    • C10L2200/0415—Light distillates, e.g. LPG, naphtha
    • C10L2200/0423—Gasoline
    • 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
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
    • C10L2200/043—Kerosene, jet fuel
    • 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
    • C10L2230/00—Function and purpose of a components of a fuel or the composition as a whole
    • C10L2230/08—Inhibitors
    • C10L2230/087—Inhibitors for inhibiting misting
    • 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
    • C10L2230/00—Function and purpose of a components of a fuel or the composition as a whole
    • C10L2230/14—Function and purpose of a components of a fuel or the composition as a whole for improving storage or transport of the fuel
    • 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
    • C10L2230/00—Function and purpose of a components of a fuel or the composition as a whole
    • C10L2230/22—Function and purpose of a components of a fuel or the composition as a whole for improving fuel economy or fuel efficiency
    • 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
    • C10L2270/00—Specifically adapted fuels
    • C10L2270/04—Specifically adapted fuels for turbines, planes, power generation
    • 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
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/24—Mixing, stirring of fuel components

Definitions

  • the present invention is directed to aviation gasoline formulations that incorporate branched aromatic compounds therein to improve the Motor Octane Number (MON) of the aviation gasoline.
  • MON Motor Octane Number
  • MON Motor Octane Number
  • a base fuel of aviation alkylate is typically mixed with an organolead octane enhancing additive and sometimes additional amounts of an aromatic component to improve the octane of the fuel.
  • organolead-based additives With the industry moving away from organolead-based additives the urgency to find alternative octane enhancers is great.
  • an organometallic manganese compound specifically methylcyclopentadienyl manganese tricarbonyl (MMT)
  • MMT methylcyclopentadienyl manganese tricarbonyl
  • Aromatic aviation gasoline additives well-known to the industry include toluene, p-xylene, and mesitylene. These aromatic compounds can increase the MON of an aviation gasoline to a desired number, but only in relatively high amounts. Furthermore, excessively high blend volumes of these components can damage seals and other elastomeric components in the fuel system. Another potential drawback to using high blend volumes of aromatics is their propensity to form smoke upon combustion.
  • the use of aromatic components in conjunction with an organomanganese antiknock such as MMT typically results in insensitivity to the organomanganese antiknock. Past research has shown that aromatic components do not respond, that is no octane enhancement is observed, to low treat rates of organomanganese compounds such as MMT.
  • EP0609089 discloses organometallic manganese complexes as octane enhancers in aviation gasoline composed of aviation alkylate and toluene.
  • the discovery set forth herein describes the use of branched aromatic compounds to synergistically cooperate with MMT to increase the MON of an aviation gasoline.
  • This branched aromatic-MMT synergy not only enhances the MON to a significantly greater degree than traditional aromatics; it will allow for the reduction of the amount of organomanganese compound under certain circumstances.
  • branched aromatic in an aviation gasoline to improve the MON of the fuel.
  • Synergies between the branched aromatic and organomanganese antiknock compound significantly enhance the MON over what is typically observed with non-branched aromatics.
  • employment of branched aromatics may in fact lower the organomanganese antiknock treat rate.
  • an aviation gasoline formulation comprises at least 20 volume percent of aviation alkylate composition and one to 50 volume percent of aromatic composition.
  • the formulation also includes a manganese-containing compound.
  • the aromatic composition includes a branched aromatic composition that is an aromatic functional group covalently bonded to a branched alkyl group.
  • the aromatic functional group may be selected from the group consisting of benzene, naphthalene and anthracene.
  • the aromatic functional group may be a heteroaromatic group that contains an atom selected from the group consisting of oxygen, nitrogen and sulfur.
  • the aromatic functional group may be a 5 or 6 membered aromatic ring.
  • the branched alkyl group may contain 3 to 15 atoms and may be formed entirely of carbon atoms.
  • the branched alkyl group may include one or more heteroatoms selected from the group consisting of oxygen, nitrogen, sulfur, silicon, phosphorus, boron, fluorine, chlorine, bromine, and iodine.
  • the branched aromatic composition comprises one to 25 volume percent of the aviation gasoline formulation.
  • the branched aromatic composition may comprise a mixture of different branched aromatic compositions.
  • the branched aromatic composition may be tert-butylbenzene.
  • the amount of manganese-containing compound which is an organomanganese is present in the amount of 1 mg Mn/L to 500 mg Mn/L. It may have a MON of the aviation gasoline of at least 99.6.
  • the aromatic composition may be present in the amount of 30 volume percent of the gasoline formulation or less and the MON of the aviation gasoline is at least 99.6.
  • a method for reducing the amount of manganese-containing engine deposits formed in the combustion of an aviation gasoline formulation includes the following steps.
  • a first aviation gasoline formulation is provided that comprises at least about 20 volume percent of aviation alkylate composition, a first amount of manganese-containing compound, and about one to 50 volume percent of unbranched aromatic compound.
  • a second aviation gasoline formulation is prepared by substituting a branched aromatic composition for at least about 25 volume percent of the unbranched aromatic compound, and at the same time incorporating only a second amount of manganese-containing compound that is less than the first amount of manganese-containing compound wherein the branched aromatic composition comprises 1 to 25 volume percent of the aviation gasoline formulation and the manganese - containing compound is an organo manganese and incorporated in the aviation gasoline in an amount from 1 mg Mn/L to 500 mg Mn/L.
  • the combustion of the second aviation gasoline formulation results in the formation of less manganese-containing engine deposits than the combustion of the first aviation gasoline formulation.
  • the high octane requirements for aviation gasoline currently a Motor Octane Number (MON) of at least 99.6 (based on ASTM D-2700), mean there is a challenge to obtain sufficient detonation resistance when formulating aviation gasoline.
  • Organometallic antiknock additives with or without a substantial aromatic fraction of the aviation gasoline formulation, present a viable pathway to achieve the at least 99.6 MON target.
  • the use of effective amounts of organomanganese are acceptable to reach octane requirements.
  • branched aromatic compounds can increase fuel octane both alone and in a mixture with an organometallic additive.
  • Particular synergistic benefits are realized when branched aromatic compounds are used in conjunction with organomanganese antiknocks.
  • a branched aromatic is defined as a compound that contains both an aromatic functional group covalently bonded to a branched alkyl group.
  • An aromatic functional group is typically benzene (single ring) but may be naphthalene (two rings), anthracene (three rings) or other polyaromatic groups.
  • a single benzene ring is one example but multiple aromatic groups are within the scope of this description.
  • Heteroaromatic groups containing oxygen, nitrogen, or sulfur are also included in the scope of this description.
  • the number of atoms in the aromatic ring includes, but is not limited to, 5 or 6 membered aromatic rings. Higher numbered rings in polyaromatic systems may also be the aromatic functional group that is described herein.
  • An unbranched aromatic is by definition a simple aromatic ring or rings with no groups bonded to it/them or other groups bonded to it/them than a branched alkyl group.
  • Commercial examples of such unbranched aromatics, in addition to the simple aromatic groups noted above, include toluene, p-xylene and mesitylene.
  • the branched alkyl group that is part of the branched aromatic described herein contains a minimum of three atoms, preferably carbon, up to 15 atoms.
  • Common examples of branched alkyl groups are iso-propyl, iso-butyl, sec-butyl, tert-butyl, iso-pentyl, neo-pentyl, tert-pentyl, and so forth.
  • Iso-propyl is a preferred example of such a branched alkyl group.
  • Tert-butyl is also a preferred example of such branched alkyl group.
  • branched alkyl groups all carbon atoms were sp 3 hybridized. Incorporation of carbon atoms exhibiting sp or sp 2 hybridization may also be used. Additionally, incorporation of heteroatoms, either as part of the alkyl chain backbone or anywhere else in the branched alkyl groups is included herein. Such heteroatoms include, but are not limited to, oxygen, nitrogen, sulfur, silicon, phosphorous, boron, fluorine, chlorine, bromine, and iodine.
  • a branched aromatic compound must have at least one of the above defined branched alkyl groups. However, branched aromatic compounds containing 2-6 additional branched alkyl groups are within the scope of this invention.
  • a compound containing a branched alkyl group for example iso-propyl, as well as a non-branched alkyl group, for example a methyl group, bonded to the aromatic ring still falls under the scope of this invention.
  • An example of this compound would be 4-tert-butyl toluene.
  • the aviation fuel composition as described herein typically contains aviation alkylate components. Those components may comprise at least 20 to 80 volume percent of the fuel.
  • Aromatic hydrocarbons are incorporated into the fuel to improve the octane rating of the fuel. These aromatic hydrocarbons are incorporated according to one example of the present invention at a rate of 1 to 30 volume percent of the fuel composition. In another example, the aromatic hydrocarbons are incorporated at a rate of 10 to 20 volume percent of the fuel composition.
  • Aviation gasoline must meet certain physical property and performance characteristics that set it apart from motor gasoline. Aviation gasoline must possess strong detonation resistance; the ASTM D-910 spec for leaded aviation gasoline quantifies this property as a Motor Octane Number of at least 99.6. A premium motor gasoline (93 Octane by R+M/2 Method) typically has a Motor Octane Number of 88, which those skilled in the art will recognize as a significant difference. Aviation gasoline furthermore requires strict adherence to minimum freeze point and specific volatility values to ensure safe in flight operation under a variety of possible conditions.
  • Motor gasoline typically comprises a number of refinery streams such as reformate, isomerate, naphtha, catalytically cracked naphtha, and alkylate, with each of these streams containing dozens, up to hundreds, of unique hydrocarbons. Due to the high demand of motor gasoline its composition can differ dramatically from region to region and refinery to refinery. Inherent technological differences between refineries, the identity of the crude oil feedstock, and refinery economics all contribute to the inherent variability of motor gasoline blends. The susceptibility of motor gasoline to MMT varies widely based on the blend volumes of refinery gasoline feedstock.
  • aromatics are not susceptible to MMT, it is difficult to identify specific molecules in motor gasoline that are synergistic with organomanganese antiknocks. Furthermore, due to the need to manage costs while meeting high demand, it is practically impossible to blend a large volume of any particular molecule into motor gasoline. Therefore, the aromatics portion of motor gasoline comprises a blend of numerous aromatic molecules.
  • aviation gasoline Since aviation gasoline must meet such stringent physical property and performance requirements, its composition is tightly controlled. Typical leaded aviation gasoline contains at least 75 vol% aviation alkylate (C5-C8 paraffins), 0-15 vol% toluene, 0-10% iso-pentane, and butane as required to meet the vapor pressure. Acknowledging aviation gasoline only contains predominantly one aromatic compound (whereas motor gasoline contains a blend of aromatic compounds), it is logical to attempt to optimize the aromatic component of aviation gasoline. Comparing Example 1 to Example 13 demonstrates the fundamental difference between aviation gasoline and motor gasoline. Example 1, representative of aviation gasoline containing only toluene as the aromatic component, exceeds the minimum MON threshold of 99.6. Example 13, representative of motor gasoline by containing a mixture of aromatic hydrocarbons, fails to meet the minimum MON threshold of 99.6. The uniquely well controlled composition of aviation gasoline allows for experimentation with novel blend components to enhance physical and performance properties such as Motor Octane Number.
  • Organomanganese antiknock additives present a viable solution to address the challenges of meeting the same minimum octane requirement as leaded aviation gasoline.
  • Organoleads antiknock compounds Since tetraethyl lead has a different response curve compared to MMT, one cannot assume simply replacing TEL with MMT will result in the same detonation resistance. The response to individual components to MMT differs from TEL.
  • toluene is susceptible to octane enhancement from TEL but shows no susceptibility to MMT.
  • Antagonism of the antiknock compound also differs - certain amines can inhibit the antiknock effectiveness of TEL but in the presence of MMT these amines will act synergistically.
  • All of the aviation gasoline referenced in this description is substantially lead-free.
  • an aviation gasoline composition is described in ASTM 4814 as substantially “lead-free” or “unleaded” if it contains 13 mg of lead or less per liter (or about 50 mg Pb/gal or less) of lead in the fuel.
  • the terms “lead-free” or “unleaded” mean about 7 mg of lead or less per liter of fuel.
  • it means an essentially undetectable amount of lead in the fuel composition. In other words, there can be trace amounts of lead in a fuel; however, the fuel is essentially free of any detectable amount of lead.
  • the amounts of organomanganese that are incorporated in the aviation gasoline is from 1 mg Mn/L to 500 mg Mn/L, or alternatively 20 to 250 mg Mn/L, or still further alternatively 25 to 225 mg Mn/L.
  • the amount of manganese may vary depending on the target octane increase in the aviation gasoline formulation.
  • organomanganese additives are typically, but not limited to, cyclopentadienyl manganese tricarbonyl compounds.
  • Cyclopentadienyl manganese tricarbonyl compounds which can be used in the practice of the fuels herein include cyclopentadienyl manganese tricarbonyl, methylcyclopentadienyl manganese tricarbonyl, dimethylcyclopentadienyl manganese tricarbonyl, trimethylcyclopentadienyl manganese tricarbonyl, tetramethylcyclopentadienyl manganese tricarbonyl, pentamethylcyclopentadienyl manganese tricarbonyl, ethylcyclopentadienyl manganese tricarbonyl, diethylcyclopentadienyl manganese tricarbonyl, propylcyclopentadienyl manganese tricarbonyl, isopropylcyclopentadienyl manganese tricarbonyl, tertbutylcyclopentadienyl manganese tricarbonyl, octylcyclopen
  • cyclopentadienyl manganese tricarbonyls which are liquid at room temperature such as methylcyclopentadienyl manganese tricarbonyl, ethylcyclopentadienyl manganese tricarbonyl, liquid mixtures of cyclopentadienyl manganese tricarbonyl and methylcyclopentadienyl manganese tricarbonyl, mixtures of methylcyclopentadienyl manganese tricarbonyl and ethylcyclopentadienyl manganese tricarbonyl, etc.
  • the aviation fuels of this invention will contain an amount of one or more of the foregoing cyclopentadienyl manganese tricarbonyl compounds sufficient to provide the requisite octane number and/or valve seat wear performance characteristics.
  • An aviation gasoline was formulated with 25 volume percent alkylate, 20 volume percent toluene, 50 volume percent isooctane, and 5 volume percent isopentane. To this gasoline blend, 225 mg Mn/L, as MMT was added. The Motor Octane Number rating of this fuel ranged from 101.0 - 101.5.
  • An aviation gasoline was formulated with 25 volume percent alkylate, 20 volume percent cumene, 50 volume percent isooctane, and 5 volume percent isopentane.
  • 225 mg Mn/L, as MMT was added to this gasoline blend.
  • the Motor Octane Number rating of this fuel was measured to be 102.5.
  • the configuration of the substituents attached to the aromatic plays an intrinsic role in enhancing the octane number of the fuel.
  • Mesitylene which contains three carbon atom substituents as methyl groups, gave a Motor Octane Rating of 101.3.
  • Cumene which also contains three carbon atom substituents except as an isopropyl group, gave a higher Motor Octane Number.
  • An aviation gasoline was formulated with 25 volume percent alkylate, 20 volume percent tert-butylbenzene, 50 volume percent isooctane, and 5 volume percent isopentane.
  • 225 mg Mn/L, as MMT was added.
  • the Motor Octane Number rating of this fuel was measured to be 104.0.
  • Aviation gasoline was formulated with 25 volume percent alkylate, 20 volume percent of either toluene or tert-butylbenzene, 50 volume percent isooctane, and 5 volume percent isopentane.
  • the Motor Octane Numbers were measured before and after the addition of 225 mg Mn/L, as MMT and are summarized in Table 2.
  • the base fuel blend containing tert-butylbenzene had a higher octane rating than the base fuel containing toluene as the aromatic component.
  • the fuel containing tert-butylbenzene saw a greater increase in Motor Octane Number despite the untreated fuel having a higher Motor Octane Number than the toluene based fuel.
  • An aviation gasoline was formulated with 25 volume percent alkylate, 20 volume percent styrene, 50 volume percent isooctane, and 5 volume percent isopentane.
  • 225 mg Mn/L, as MMT was added to this gasoline blend.
  • the Motor Octane Number rating of this fuel was measured to be 100.6. This demonstrates adding unsaturated substituents to the aromatic ring will yield fuels with acceptable Motor Octane Numbers.
  • An aviation gasoline was formulated with 80 volume percent alkylate, 15 volume percent toluene, and 5 volume percent isopentane. To this gasoline blend, 125 mg Mn/L, as MMT was added. The Motor Octane Number of this fuel was 98.0. Replacing 15 volume percent toluene with 15 volume percent tert-butylbenzene raises the Motor Octane Number to 100.3.
  • a conventional aviation gasoline formulation can be modified with substituting branched aromatic compositions for some or all of conventional unbranched aromatics and then using less manganese-containing compounds (e.g., MMT) as an octane enhancer.
  • a first aviation gasoline formulation may contain at least 20 volume percent of aviation alkylate (in the example above, 25 volume percent). This first aviation gasoline formulation would also include a first amount of manganese-containing compound to reach a desired MON.
  • the first aviation gasoline might include one to 50 volume percent of unbranched aromatic composition.
  • This Example 9 demonstrates that the unbranched aromatic can be substituted in whole or in part, or alternatively at least 25 volume percent, with a branched aromatic composition.
  • Branched aromatics other than tert-butylbenzene are effective as well.
  • An aviation gasoline was formulated to contain 22 volume percent alkylate, 50 volume percent isooctane, 17.5 volume percent p-cymene, and 10.5 volume percent isopentane.
  • the Motor Octane Number of this fuel without MMT is 96.3.
  • the Motor Octane Number rises to 102.1.
  • Branched aromatics other than tert-butylbenzene are effective as well.
  • An aviation gasoline was formulated to contain 25 volume percent alkylate, 50 volume percent isooctane, 5 volume percent isopentane, and 20 volume percent aromatic.
  • the Mn treat rate, as MMT, was held constant at 225 mg Mn/L.
  • the Motor Octane Number of the resultant formulations was measured by the ASTM D2700 method and summarized in Table 6.
  • Aromatic 150 Solvent consists of a blend of dozens of alkyl and branched alkyl substituted aromatic compounds. To this base fuel, 225 mg Mn/L as MMT was added. The Motor Octane Number of this fuel was measured at 99.1.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Catalysts (AREA)

Claims (12)

  1. Formulation d'essence d'aviation comprenant :
    au moins 20 pour cent en volume de composition d'alkylate d'aviation :
    un composé contenant du manganèse ; et
    un à 50 pour cent en volume de composition aromatique, dans laquelle la composition aromatique inclut une composition aromatique ramifiée qui est un groupe fonctionnel aromatique lié par covalence à un groupe alkyle ramifié, dans laquelle la composition aromatique ramifiée constitue 1 à 25 pour cent en volume de la formulation d'essence d'aviation et le composé contenant du manganèse est un organomanganèse et est incorporé dans l'essence d'aviation en une quantité allant de 1 mg de Mn/L à 500 mg de Mn/L.
  2. Formulation d'essence d'aviation selon la revendication 1, dans laquelle le groupe fonctionnel aromatique est choisi dans le groupe constitué de benzène, naphtalène et anthracène.
  3. Formulation d'essence d'aviation selon la revendication 1, dans laquelle le groupe fonctionnel aromatique est un groupe hétéroaromatique qui contient un atome choisi dans le groupe constitué d'oxygène, azote et soufre.
  4. Formulation d'essence d'aviation selon la revendication 1, dans laquelle le groupe fonctionnel aromatique est un noyau aromatique à 5 ou 6 chaînons.
  5. Formulation d'essence d'aviation selon la revendication 1, dans laquelle le groupe alkyle ramifié contient 3 à 15 atomes.
  6. Formulation d'essence d'aviation selon la revendication 5, dans laquelle le groupe alkyle ramifié est formé entièrement d'atomes de carbone.
  7. Formulation d'essence d'aviation selon la revendication 5, dans laquelle le groupe alkyle ramifié inclut un ou plusieurs hétéroatomes choisis dans le groupe constitué d'oxygène, azote, soufre, silicium, phosphore, bore, fluor, chlore, brome et iode.
  8. Formulation d'essence d'aviation selon la revendication 1, dans laquelle la composition aromatique ramifiée comprend un mélange de différentes compositions aromatiques ramifiées.
  9. Formulation d'essence d'aviation selon la revendication 1, dans laquelle la composition aromatique ramifiée est du tert-butylbenzène.
  10. Formulation d'essence d'aviation selon la revendication 1, dans laquelle la quantité de composé contenant du manganèse est présente à 500 mg de Mn/L ou moins, et l'indice d'octane moteur (MON) de l'essence d'aviation est d'au moins 99,6.
  11. Formulation d'essence d'aviation selon la revendication 1, dans laquelle la composition aromatique est présente dans la quantité de 30 pour cent en volume de la formulation d'essence ou moins, et l'indice d'octane moteur (MON) de l'essence d'aviation est d'au moins 99,6.
  12. Procédé de réduction de la quantité de dépôts de moteur contenant du manganèse formés dans la combustion d'une formulation d'essence d'aviation, le procédé comprenant les étapes consistant à :
    fournir une première formulation d'essence d'aviation qui comprend au moins 20 pour cent en volume de composition d'alkylate d'aviation, une première quantité d'un composé contenant du manganèse, et un à 50 pour cent en volume d'un composé aromatique non ramifié ;
    avant mélange de la première formulation d'essence d'aviation, préparer une deuxième formulation d'essence d'aviation en remplaçant par une composition aromatique ramifiée au moins 25 pour cent en volume de la composé aromatique non ramifié et en incorporant en même temps seulement une deuxième quantité de composé contenant du manganèse qui est inférieure à la première quantité de composé contenant du manganèse, dans lequel la composition aromatique ramifiée constitue 1 à 25 pour cent en volume de la formulation d'essence d'aviation et le composé contenant du manganèse est un organomanganèse et est incorporé dans l'essence d'aviation en une quantité allant de 1 mg de Mn/L à 500 mg de Mn/L ;
    dans lequel la combustion de la deuxième formulation d'essence d'aviation entraîne la formation de moins de dépôts de moteur contenant du manganèse que la combustion de la première formulation d'essence d'aviation.
EP17204818.3A 2016-12-01 2017-11-30 Carburant d'aviation contenant des composés aromatiques ramifiés comprenant un rehausseur d'octane de manganèse Active EP3330344B1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US15/366,346 US20180155648A1 (en) 2016-12-01 2016-12-01 Aviation Gasoline Containing Branched Aromatics with a Manganese Octane Enhancer

Publications (2)

Publication Number Publication Date
EP3330344A1 EP3330344A1 (fr) 2018-06-06
EP3330344B1 true EP3330344B1 (fr) 2020-01-08

Family

ID=60569707

Family Applications (1)

Application Number Title Priority Date Filing Date
EP17204818.3A Active EP3330344B1 (fr) 2016-12-01 2017-11-30 Carburant d'aviation contenant des composés aromatiques ramifiés comprenant un rehausseur d'octane de manganèse

Country Status (9)

Country Link
US (1) US20180155648A1 (fr)
EP (1) EP3330344B1 (fr)
CN (1) CN108130142B (fr)
AU (1) AU2017268577B2 (fr)
BR (1) BR102017025940B1 (fr)
CA (1) CA2986857C (fr)
CL (1) CL2017003056A1 (fr)
MX (1) MX2017015555A (fr)
RU (1) RU2017141731A (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113736526B (zh) * 2021-10-12 2023-01-31 华东理工大学 烷烃组合物、含该烷烃组合物的100号无铅航空汽油组合物及其生产方法

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6238446B1 (en) * 1991-10-28 2001-05-29 Ethyl Petroleum Additives, Inc. Unleaded aviation gasoline
US6187064B1 (en) * 1991-10-28 2001-02-13 Ethyl Petroleum Additives, Inc. Unleaded aviation gasoline
US5851241A (en) * 1996-05-24 1998-12-22 Texaco Inc. High octane unleaded aviation gasolines
US20020045785A1 (en) * 1996-11-18 2002-04-18 Bazzani Roberto Vittorio Fuel composition
GB9922553D0 (en) * 1999-09-23 1999-11-24 Bp Oil Int Fuel compositions
US7462207B2 (en) * 1996-11-18 2008-12-09 Bp Oil International Limited Fuel composition
US7862629B2 (en) * 2004-04-15 2011-01-04 Exxonmobil Research And Engineering Company Leaded aviation gasoline
FR2894976B1 (fr) * 2005-12-16 2012-05-18 Total France Essence aviation sans plomb
CN104593101B (zh) * 2013-10-31 2018-03-30 国际壳牌研究有限公司 高辛烷值无铅航空汽油
CN104711053A (zh) * 2013-12-11 2015-06-17 张希顺 一种清洁燃油抗爆剂

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
CL2017003056A1 (es) 2018-05-11
CA2986857C (fr) 2020-12-29
AU2017268577A1 (en) 2018-06-21
CA2986857A1 (fr) 2018-06-01
CN108130142B (zh) 2020-11-13
RU2017141731A3 (fr) 2020-04-21
BR102017025940A2 (pt) 2018-06-19
RU2017141731A (ru) 2019-05-31
AU2017268577B2 (en) 2020-01-30
US20180155648A1 (en) 2018-06-07
BR102017025940B1 (pt) 2022-07-12
CN108130142A (zh) 2018-06-08
EP3330344A1 (fr) 2018-06-06
MX2017015555A (es) 2018-11-09

Similar Documents

Publication Publication Date Title
US6039772A (en) Non leaded fuel composition
US6767372B2 (en) Aviation gasoline containing reduced amounts of tetraethyl lead
EP0697033B1 (fr) Essence d'aviation sans plomb
EP1841841B1 (fr) Essence d'aviation au plomb amelioree
US6238446B1 (en) Unleaded aviation gasoline
EP0235280B2 (fr) Composition de carburant sans plomb
US3224848A (en) Gasoline composition
US2765220A (en) Lead scavenger compositions
US6187064B1 (en) Unleaded aviation gasoline
EP3330344B1 (fr) Carburant d'aviation contenant des composés aromatiques ramifiés comprenant un rehausseur d'octane de manganèse
US2771348A (en) Stabilized cracked petroleum fractions
US2860958A (en) Antiknock compositions
US2897067A (en) Alcohol-containing gasoline composition
US3009793A (en) Motor fuel containing synergistic anti-knock additive
JP3478825B2 (ja) 無鉛ｍｍｔ燃料組成物
US3065065A (en) Gasoline composition
US2901336A (en) Antiknock compositions
US2948600A (en) Antiknock compositions
US4295861A (en) Motor fuel
US3353938A (en) Antiknock compositions and motor fuels containing them
US3421867A (en) Saturated aliphatic hydrocarbon gasoline
US4280458A (en) Antiknock component
US3272606A (en) Antiknock compositions
US3010980A (en) Trialkyl lead selenides
US3261674A (en) Stabilized gasoline antiknock compositions and gasoline containing same

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

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

Free format text: STATUS: THE APPLICATION HAS BEEN PUBLISHED

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL 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 RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

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

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20181206

RBV Designated contracting states (corrected)

Designated state(s): AL 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 RS SE SI SK SM TR

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: 20190205

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTC Intention to grant announced (deleted)
INTG Intention to grant announced

Effective date: 20190705

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): AL 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 RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602017010655

Country of ref document: DE

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: 1222715

Country of ref document: AT

Kind code of ref document: T

Effective date: 20200215

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20200108

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

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: 20200531

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: 20200108

Ref country code: RS

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: 20200108

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: 20200408

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: 20200108

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: 20200108

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

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: 20200409

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: 20200408

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: 20200508

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: 20200108

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: 20200108

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: 20200108

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602017010655

Country of ref document: DE

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

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: 20200108

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: 20200108

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: 20200108

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: 20200108

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: 20200108

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: 20200108

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: 20200108

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

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1222715

Country of ref document: AT

Kind code of ref document: T

Effective date: 20200108

26N No opposition filed

Effective date: 20201009

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

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: 20200108

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

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: 20200108

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: 20200108

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: 20200108

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

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: 20201130

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

Ref country code: CH

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

Effective date: 20201130

Ref country code: LI

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

Effective date: 20201130

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: IE

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

Effective date: 20201130

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: 20200108

Ref country code: MT

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: 20200108

Ref country code: CY

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: 20200108

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: 20200108

Ref country code: AL

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: 20200108

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

Ref country code: GB

Payment date: 20231127

Year of fee payment: 7

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

Ref country code: IT

Payment date: 20231122

Year of fee payment: 7

Ref country code: FR

Payment date: 20231127

Year of fee payment: 7

Ref country code: DE

Payment date: 20231129

Year of fee payment: 7

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

Ref country code: BE

Payment date: 20231127

Year of fee payment: 7