[go: up one dir, main page]

EP2108032B1 - Unverbleite kraftstoffzusammensetzungen - Google Patents

Unverbleite kraftstoffzusammensetzungen Download PDF

Info

Publication number
EP2108032B1
EP2108032B1 EP06846540.0A EP06846540A EP2108032B1 EP 2108032 B1 EP2108032 B1 EP 2108032B1 EP 06846540 A EP06846540 A EP 06846540A EP 2108032 B1 EP2108032 B1 EP 2108032B1
Authority
EP
European Patent Office
Prior art keywords
vol
fuel composition
unleaded fuel
octane
composition according
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
EP06846540.0A
Other languages
English (en)
French (fr)
Other versions
EP2108032A1 (de
Inventor
Jörg LANDSCHOF
Michael Clifford Macknay
Timothy Michael Shea
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.)
Shell Internationale Research Maatschappij BV
Original Assignee
Shell Internationale Research Maatschappij BV
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 Shell Internationale Research Maatschappij BV filed Critical Shell Internationale Research Maatschappij BV
Priority to EP12185306A priority Critical patent/EP2537913A1/de
Publication of EP2108032A1 publication Critical patent/EP2108032A1/de
Application granted granted Critical
Publication of EP2108032B1 publication Critical patent/EP2108032B1/de
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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • C10L1/023—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for spark ignition
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/10—Use of additives to fuels or fires for particular purposes for improving the octane number

Definitions

  • the present application relates to unleaded fuel compositions.
  • the octane rating of the fuel must be high enough to prevent knocking.
  • Gasolines sold at service stations typically have an octane rating of from about 87 to about 93. Fuels having such octane ratings are satisfactory for most automotive engines.
  • EP 1 650 289 , US 2006/0123696 , US 5 470 358 and US 5 284 984 disclose unleaded duel compositions.
  • An unleaded fuel composition comprising: 25 vol.% or more of alkylated benzenes comprising alkyl groups having from 1 to 4 carbon atoms; 5 vol.% or more of one or more aromatic amines; and, an isoparaffin composition selected from the group consisting of alkylate, a combination of isoparaffins having a total number of carbon atoms of 11 or less, and combinations thereof.
  • the present application provides unleaded fuel compositions having an octane rating of 105 or more.
  • the present application provides unleaded fuel compositions having an octane rating greater than 105.
  • the present application provides unleaded fuel compositions having an octane rating of 106 or more.
  • the present application also provides unleaded fuel compositions having an octane rating of 110 or more.
  • the present application also provides an unleaded fuel composition
  • an unleaded fuel composition comprising: 25 vol.% or more of alkylated benzenes comprising alkyl groups having from 1 to 4 carbon atoms; 5 vol.% or more of one or more aromatic amines; and, an isoparaffin composition selected from the group consisting of alkylate, a combination of isoparaffins having a total number of carbon atoms of 11 or less, and combinations thereof.
  • the present application also provides an unleaded fuel composition comprising: from about 40 vol.% to about 50 vol.% alkylate; from about 30 vol.% to about 40 vol.% toluene; from about 10 vol.% to about 20 vol.% m-xylene; and, from 2 vol.% to about 12 vol.% aniline.
  • the present application also provides an unleaded fuel composition comprising: about 44 vol.% alkylate comprising about 70 vol.% or more isoparaffins having a total of 8 carbon atoms; about 34 vol.% toluene; about 15 vol.% m-xylene; and, about 7 vol.% aniline.
  • the present application provides unleaded fuel compositions having an octane rating which is higher than typically demonstrated by similar unleaded fuels.
  • the unleaded fuels of the present application comprise aromatic amine, which is believed to contribute to a higher octane rating.
  • the unleaded fuel compositions it is advantageous for the unleaded fuel compositions to have an octane rating sufficiently high to prevent knocking. In high performance applications, it is advantageous for unleaded fuel compositions to have an octane rating sufficiently high to boost power output from the high performance engine. In one embodiment, the application provides an unleaded racing fuel having an octane rating sufficiently high to boost the power output from a racing engine.
  • the octane rating of a fuel composition generally is calculated as the sum of the Research Octane Number (RON) and the Motor Octane Number (MON) divided by 2, i.e., (R+M)/2. Unless otherwise indicated, the Research Octane Number (RON) is determined according to method ASTM D-2699-04a (2004) and the Motor Octane Number (MON) is determined according to method ASTM D-2700-04a (2004), both incorporated by reference.
  • the unleaded fuel composition of the present application has an octane rating of about 105 or more. In one embodiment, the unleaded fuel composition has an octane rating of greater than 105. In another embodiment, the unleaded fuel composition of the present application has an octane rating of about 106 or more. In one embodiment, the unleaded fuel composition has an octane rating of about 110 or more.
  • the unleaded fuel composition optionally comprises one or more oxygenate octane booster.
  • the unleaded fuel composition also optionally comprises one or more additional additives.
  • the unleaded fuel composition comprises a combination of alkylated benzenes.
  • the unleaded fuel composition comprises about 25 vol.% or more of a combination of alkylated benzenes.
  • vol.% is based on the total volume of the unleaded fuel composition, unless otherwise indicated.
  • the unleaded fuel composition comprises about 40 vol.% or more alkylated benzenes.
  • the unleaded fuel composition comprises about 60 vol.% or less alkylated benzenes. In one embodiment, the unleaded fuel composition comprises about 55 vol.% or less alkylated benzenes. In yet another embodiment, the unleaded fuel composition comprises about 50 vol.% or less alkylated benzenes.
  • Suitable alkylated benzenes have the following general structure: wherein R, R 1 , and R 2 are selected from the group consisting of hydrogen and alkyl groups having from 1 to 4 carbon atoms, provided that at least one of R, R 1 , and R 2 is an alkyl group. In one embodiment, R, R 1 , and R 2 are selected from the group consisting of hydrogen and alkyl groups having from 1 to 2 carbon atoms. In one embodiment, R, R 1 , and R 2 are selected from the group consisting of hydrogen and methyl groups. In one embodiment, the alkylated benzene is mono-alkylated benzene. In another embodiment, the alkylated benzene is a di-alkylated benzene. In another embodiment, the alkylated benzene is a tri-alkylated benzene. In one embodiment, one or more of R, R 1 , and R 2 are methyl groups.
  • the alkylated benzenes are a combination of mono-alkylated benzene, di-alkylated benzene, and tri-alkylated benzene.
  • the unleaded fuel composition comprises a combination of monomethyl benzene and dimethyl benzene. In one embodiment, the combination further comprises trimethyl benzene. In one embodiment, the unleaded fuel composition comprises a combination of xylene and toluene. In one embodiment, the unleaded fuel composition further comprises 1,3,5-trimethylbenzene.
  • the unleaded fuel composition also comprises one or more aromatic amine.
  • the unleaded fuel composition For lower performance applications, it is possible for the unleaded fuel composition to comprise about 0.1 vol.% or more of one or more aromatic amine. This is particularly true where the isoparaffin comprises the less expensive alkylate.
  • the unleaded fuel composition comprises 5 vol.% or more of the aromatic amine. In one embodiment, the unleaded fuel composition comprises greater 5 vol.% of the aromatic amine. In one embodiment, the unleaded fuel composition comprises about 6 vol.% or more of the aromatic amine. In another embodiment, the unleaded fuel composition comprises about 7 vol.% or more of the aromatic amine.
  • the unleaded fuel composition comprises about 15 vol.% or less of the aromatic amine. In one embodiment, the unleaded fuel composition comprises from about 10 vol.% or less of the aromatic amine. In one embodiment, the unleaded fuel composition comprises 8 vol.% or less of the aromatic amine. In one embodiment, the unleaded fuel composition contains about 7 vol.% of the aromatic amine.
  • aromatic amine refers to one or more aromatic amines having the following general structure: wherein R 3 , R 4 and R 5 independently are selected from the group consisting of hydrogen and alkyl groups having from about 1 to 4 carbon atoms.
  • R 3 is hydrogen.
  • the alkyl groups have from about 1 to 2 carbon atoms.
  • the alkyl groups are methyl groups.
  • R 3 , R 4 and R 5 are hydrogens.
  • the aromatic amine has one or more alkyl substituents on the aromatic ring.
  • the alkyl group may be at any position relative to the nitrogen containing substituent.
  • the alkyl group is at a meta- position relative to the nitrogen containing substituent.
  • the alkyl group is at a para- position relative to the nitrogen containing substituent.
  • the nitrogen bears an alkyl group.
  • the octane rating of the unleaded fuel may not be as high.
  • Aromatic amines used in the examples have the following general structure:
  • the isoparaffin composition isoparaffin composition
  • the unleaded fuel composition also comprises an isoparaffin composition.
  • the unleaded fuel composition comprises about 40 vol.% or more of the isoparaffin composition. In one embodiment, the unleaded fuel composition comprises about 45 vol.% or more of the isoparaffin composition. In one embodiment, the unleaded fuel composition comprises about 50 vol.% or more of the isoparaffin composition.
  • the unleaded fuel composition comprises about 80 vol.% or less of the isoparaffin composition. In one embodiment, the unleaded fuel composition comprises from about 70 vol.% or less of the isoparaffin composition. In one embodiment, the unleaded fuel composition comprises about 60 vol.% or less of the isoparaffin composition.
  • Suitable isoparaffin compositions comprise alkylate, a combination of isoparaffins, and combinations thereof.
  • the isoparaffin composition comprises alkylate.
  • alkylate typically refers to branched-chain paraffin.
  • the branched-chain paraffin typically is derived from the reaction of isoparaffin with olefin. Alkylation is described, for example, in J. Gary, et al. Petroleum Refining, Technology and Economics (2d Ed. 1984) Chapter 10, pp. 159-183 , and in Kirk Othmer. Concise Encyclopedia of Chemical Technology (4th Ed. 1999) Vol. 1, p. 75-76 .
  • alkylate refers to hydrocarbon compositions used for fuel applications (a) having at least 55 normalized vol.% C5 - C10 iso-paraffins measured pursuant to ASTM test method D-6730-01 (2001), or having at least 55 vol.% C5-C10 iso-paraffins measured pursuant to ASTM test method D-6733-01 (2001).
  • the alkylate is a refinery grade alkylate formed by the reaction of a C3-C5 stream with isobutene.
  • the alkylate advantageously comprises about 70 vol.% or more isoparaffins having a total of 8 carbon atoms. In one embodiment, the alkylate advantageously comprises greater than 70 vol.% isoparaffins having a total of 8 carbon atoms. In one embodiment, the alkylate advantageously comprises about 73 vol.% or more isoparaffins having a total of 8 carbon atoms. In one embodiment, the alkylate comprises about 90 vol.% or less isoparaffins having a total of 8 carbon atoms. In yet another embodiment, the alkylate comprises about 85 vol.% or less isoparaffins.
  • the alkylate comprises less than 5 vol.% isoparaffins having a total of 6-7 carbon atoms.
  • Suitable alkylate typically has a RON of, for example, from about 90 to about 95.
  • Suitable alkylate typically has a MON of, for example, from about 88 to about 95.
  • Suitable alkylate typically has an octane rating of, for example, from about 90 to about 95.
  • Suitable alkylates can be obtained from a variety of sources, including Solvents & Chemicals, Pearland, Texas; Equistar Chemicals; and, Texas Petrochemicals.
  • the isoparaffin composition comprises a combination of isoparaffins.
  • Suitable isoparaffins have the following general structure: wherein R 6 , R 7 , R 8 , R 9 , R 10 , and R 11 independently are selected from the group consisting of hydrogen and alkyl groups having from about 1 to about 7 carbon atoms, provided that the total number of carbon atoms is 11 or less.
  • R 6 , R 7 , R 8 , R 9 , R 10 , and R 11 independently are selected from the group consisting of hydrogen and methyl groups.
  • the unleaded fuel comprises a combination of iso-pentane and iso-octane.
  • the unleaded fuel composition comprises primarily trimethyl pentane.
  • the unleaded fuel composition comprises primarily 2,2,4-trimethyl pentane.
  • the isoparaffins are commercially available from a variety of sources and/or may be made by known processes. Examples of suitable preparations are described in F. L. Howard, et al. J. Res. Nat. Bur. Standards Research Paper RP1779, Vol. 38 (March 1947) pp. 365-395 , incorporated herein by reference. The isoparaffins made by the above processes may be used as a blend or purified further.
  • the isoparaffins may be obtained by fractional distillation of refinery streams, e.g., straight run gasolines, or alkylation products.
  • Other known methods of making the isoparaffins include, for example, reaction of alkyl metallic compounds (Grignard reagents) with carbonyl compounds, such as aldehydes, ketones, esters, or anhydrides, to form branched chain carbinols, which are dehydrated to the corresponding olefin and thereafter hydrogenated to the alkane.
  • alkyl metallic compounds such as aldehydes, ketones, esters, or anhydrides
  • the unleaded fuel composition optionally comprises oxygenate octane booster.
  • the oxygenate octane booster may be any liquid organic molecule containing one or more alkyl group and one or more oxygen atom. Suitable oxygenate octane boosters include, for example, ethers and alcohols.
  • the oxygenate octane booster is one or more alkyl ether.
  • the alkyl ether comprises an alkyl group having from 1 to 6 carbon atoms.
  • the alkyl group has from 3 to 6 carbon atoms.
  • the alkyl group is a branched chain alkyl group having from 3 to 6 carbon atoms.
  • the alkyl group is a tertiary alkyl group having from 4 to 6 carbon atoms. Suitable tertiary alkyl groups include, for example, tert-butyl groups and tert-amyl groups.
  • the alkyl ether is dialkyl ether. In one embodiment, the alkyl ether is asymmetric dialkyl ether. In one embodiment, the dialkyl ether comprises a tertiary alkyl group and a second alkyl group having from 1 to 6 carbon atoms. In one embodiment, the dialkyl ether comprises a first tertiary alkyl group and second alkyl group having from 1 to 3 carbon atoms. In one embodiment, the second alkyl group is a linear alkyl group. In one embodiment, the second alkyl group is selected from the group consisting of a methyl group and an ethyl group. Specific examples of suitable alkyl ethers include methyl tertiary butyl ether (MTBE), ethyl tertiary butyl ether, and methyl tertiary amyl ether.
  • MTBE methyl tertiary butyl ether
  • ethyl tertiary butyl ether
  • the use of an oxygenate octane booster in the unleaded fuel composition is optional.
  • the unleaded fuel composition may comprise, for example, 25 vol.% or less oxygenate octane booster. In one embodiment, the unleaded fuel composition comprises about 20 vol.% or less oxygenate octane booster. In one embodiment, the unleaded fuel composition comprises about 16 vol.% or less oxygenate octane booster. In one embodiment, the unleaded fuel composition comprises about 8 vol.% or more oxygenate octane booster. In one embodiment, the unleaded fuel composition comprises about 10 vol.% or more oxygenate octane booster. In another embodiment, the unleaded fuel composition comprises about 12 vol.% or more oxygenate octane booster.
  • Suitable oxygenate octane boosters are made using known processes and are available commercially from a variety of sources.
  • the unleaded fuel composition optionally may comprise a variety of other components as long as they are suitable for combustion in an automotive spark ignition engine and they do not have a significant impact on octane number.
  • a component does not have a significant impact on octane number if, in the concentration(s) employed, the octane number is not raised or lowered by more than about 1.0 unit, as calculated by ASTM D-2699-04a (2004).
  • Suitable components include, for example, motor gasoline additives as listed in ASTM D-4814-04 or as specified by a regulatory body, e.g., U.S. California Air Resources Board (CARB) or the U.S. Environmental Protection Agency (EPA).
  • a regulatory body e.g., U.S. California Air Resources Board (CARB) or the U.S. Environmental Protection Agency (EPA).
  • Examples of other components suitable for use in the unleaded fuel composition include other paraffins, aromatic hydrocarbons, alcohols, ethers, and/or esters.
  • Refinery streams that may be used in the unleaded fuel include, for example, distillation products and reaction products from a refinery such as catalytic reformate, heavy catalytic cracked spirit, light catalytic cracked spirit, straight run gasoline, isomerate, light reformate, light hydrocrackate, and naphtha.
  • Other gasoline components include olefins (in particular with one double bond per molecule). Examples include liquid alkene having from 5 to 10 carbon atoms. In one embodiment, the liquid alkene has from 6 to 8 carbon atoms. The liquid alkene may be linear or branched. Specific examples of suitable liquid alkenes include pentene, isopentene, hexene, isohexene, heptene, and mixtures thereof.
  • paraffins examples include, for example, straight-chain paraffins and cyclic paraffins.
  • Straight chain paraffins are sometimes also referred to as normal paraffins.
  • the fuel also may contain lead replacement additives and/or other common additives which have no significant impact on octane value, for example, dyes, deicing agents, agents for preventing exhaust valve seat wear, anti-oxidants, corrosion inhibitors, anti-static additives, detergents and the like.
  • lead replacement additives and/or other common additives which have no significant impact on octane value, for example, dyes, deicing agents, agents for preventing exhaust valve seat wear, anti-oxidants, corrosion inhibitors, anti-static additives, detergents and the like.
  • the unleaded fuel composition may not comprise any additive.
  • the unleaded fuel composition also may comprise one or more additives.
  • the unleaded fuel composition typically comprises about 1000 ppm or less total amount of additives.
  • each additive typically is present in an amount of about 0.1 ppm or more.
  • each additive is present in an amount of about 0.5 ppm or more.
  • each additive is present in an amount of about 1 ppm or more.
  • each additive is present in an amount of 100 ppm or less.
  • each additive is present in an amount of 50 ppm or less.
  • each additive is present in an amount of 20 ppm or less.
  • the unleaded fuel composition comprises lead replacement additive. In one embodiment, the unleaded fuel composition comprises antioxidant. In one embodiment, the unleaded fuel composition comprises detergent additive. In one embodiment, the unleaded fuel composition comprises a combination of lead replacement additive, antioxidant, and detergent additive.
  • the unleaded fuel composition typically comprises, for example, about 20 mg/kg or more lead replacement additive. In one embodiment, the unleaded fuel composition comprises from about 25 mg/kg or more lead replacement additive. In one embodiment, the unleaded fuel composition comprises about 30 mg/kg or more lead replacement additive. In one embodiment, the unleaded fuel composition comprises about 60 mg/kg or less lead replacement additive. In one embodiment, the unleaded fuel composition comprises about 55 mg/kg or less lead replacement additive. In one embodiment, the unleaded fuel composition comprises about 50 mg/kg or less lead replacement additive.
  • the unleaded fuel composition typically comprises, for example, about 10 mg/kg or more antioxidant. In one embodiment, the unleaded fuel composition comprises about 15 mg/kg or more antioxidant. In one embodiment, the unleaded fuel composition comprises about 20 mg/kg or more antioxidant. In one embodiment, the unleaded fuel composition comprises about 50 mg/kg or less antioxidant. In one embodiment, the unleaded fuel composition comprises about 45 mg/kg or less antioxidant. In one embodiment, the unleaded fuel composition comprises about 40 mg/kg or less antioxidant.
  • the unleaded fuel composition typically comprises, for example, about 0.011 kg/m 3 (0.05 g/gallon) or more detergent additive. In one embodiment, the unleaded fuel composition comprises about 0.018 kg/m 3 (0.08 g/gallon) or more detergent additive. In one embodiment, the unleaded fuel composition comprises about 0.022 kg/m 3 (0.1 g/gallon) or more detergent additive. In one embodiment, the unleaded fuel composition comprises about 0.88 kg/m 3 (4g/ gallon) or less detergent additive. In one embodiment, the unleaded fuel composition comprises about 0.77 kg/m 3 (3.5 g/gallon) or less detergent additive. In one embodiment, the unleaded fuel composition comprises about 0.66kg/m 3 (3 g/gallon) or less detergent additive.
  • the unleaded fuel composition comprises: about 40 mg/kg lead replacement additive; about 30 mg/kg antioxidant; and, from about 1 to about 2 g/gallon detergent additive.
  • Suitable additives are made using known processes and are available commercially from a variety of sources.
  • the unleaded fuel composition comprises: 25 vol.% or more of alkylated benzenes comprising alkyl groups having from 1 to 4 carbon atoms; 5 vol. % or more of one or more aromatic amines; and, an isoparaffin composition selected from the group consisting of alkylate, a combination of isoparaffins having a total number of carbon atoms of 11 or less, and combinations thereof.
  • An unleaded fuel composition not according to the invention comprises: from about 20 vol.% to about 60 vol.% of the combination of alkylated benzenes; from greater than 5 vol.% to about 15 vol.% of the one or more aromatic amine; and, from about 40 vol.% to about 80 vol.% of the isoparaffin composition.
  • the unleaded fuel composition comprises greater than 5 vol.% of the aromatic amine.
  • the unleaded fuel composition comprises about 7 vol.% or more of the aromatic amine.
  • the unleaded fuel composition comprises about 10 vol.% or less of the aromatic amine.
  • the unleaded fuel composition comprises about 7 vol.% or less of the aromatic amine.
  • the unleaded fuel composition contains about 7 vol.% of the aromatic amine. In one embodiment, the unleaded fuel composition further comprises one or more oxygenate octane booster. In one embodiment, the combination of alkylated benzene comprises from 21 vol.% to 25 vol.% toluene; and from 19 vol.% to 24 vol.% m-xylene, based on the total weight of the unleaded fuel composition.
  • the alkylate comprises 70 vol.% or more isoparaffins having a total of 8 carbon atoms.
  • the unleaded fuel composition comprises from 40 vol.% to 60 vol.% of the combination of alkylated benzene; 15 vol..% or less of the one or more aromatic amines; and, from 40 vol. % to 50 vol. % alkylate.
  • the unleaded fuel composition comprises: alkylate; a combination of alkylated benzenes; and, one or more aromatic amines.
  • the unleaded fuel composition comprises: from about 40 vol.% to about 50 vol.% alkylate, preferably 42 vol.% to 50 vol.% alkylate; from about 30 vol.% to about 40 vol.% toluene, preferably 32 vol.% to 36 vol.% toluene; from about 10 vol.% to about 20 vol.% m-xylene, preferably 13 vol. % to 17 vol.% m-xylene; and, from about 2 vol.% to about 12 vol.% aniline, prefereably from 5 vol.% to 9 vol.% aniline.
  • the unleaded fuel comprises: 44 vol.% alkylate comprising 70 vol.% or more isoparaffins having a total of 8 carbon atoms; 34 vol.% toluene; 15 vol.% m-xylene, and 7 vol.% aniline. In one embodiment, the unleaded fuel composition comprises about 5 vol% or more aniline.
  • the unleaded fuel composition comprises additional additives.
  • the unleaded fuel composition a combination of lead replacement additive, antioxidant, and detergent additive.
  • the unleaded fuel composition also optionally may comprise one or more oxygenate octane booster.
  • Jessup relates to fuels for high performance engines and for racing engines in particular.
  • Jessup describes fuel compositions having octane ratings of "at least about 100 ... comprised of toluene and alkylate and at least two further components selected from the group consisting of [isopentane], n-butane and methyl tertiary butyl ether.”
  • Jessup Tables 4 and 7 show ingredients and concentration ranges which meet minimum octane rating requirements of about 100. The highest “Actual Octane Value" that Jessup appears to achieve using the blends is 101.
  • Bazzani U.S.Patent Application 2003/0183554 to R. Bazzani, et al.
  • the composition may comprise at least one aromatic compound, for example having 6-9 carbons, preferably an alkyl aromatic compound such as toluene or o, m, or p xylene or a mixture thereof or a trimethyl benzene.
  • Aromatic amines may be used "in an amount of less than 5% by volume for mogas or avgas, and are preferably substantially absent ... e.g., less than 100 ppm.” Bazzani, paragraph [0051] .
  • Bazzani states with respect to the compositions of Bazzani's "part (a)" that the ROAD value (or octane rating) "is usually 85-115 e.g. 98-115 or preferably 85-98 such as 85-95 e.g. 85-90, or 90-95 or 95-98.
  • Preferred gasoline compositions have ...ROAD 85-90 ...ROAD 85-95 or ... ROAD 90-95.”
  • the highest ROAD value actually reported in the Examples relevant to "part (a)” is 97.25 (Table 1, p. 12).
  • Bazzani states with respect to the compositions in "part (b)" that "the ROAD value is usually 85-107 e.g. 98-106 or preferably 85-98 such as 85-95 e.g. 85-90, or 90-95 or 95-98.
  • Preferred gasoline compositions have ... ROAD 85-90, or .. . ROAD 85-95 or ...ROAD 91-96.”
  • Bazzani paragraph [0238].
  • Bazzani states that the compositions of "part (b)” can reach a ROAD value over 105
  • Bazzani does not state that the compositions tested in the relevant Examples either (a) contained 5 vol.% or more aromatic amine, or (b) had a ROAD value of greater than 105.
  • the RON and MON values reported in the Examples relevant to part (b) are below 100, and therefore the ROAD value is below 100.
  • Bazzani pp. 31-34.
  • Bazzani states with respect to the compositions in "part (c)" that "the ROAD value is usually 85-110 or 85-107 e.g. 98-106 or 102-108 or 85-95. Preferred gasoline compositions have ... ROAD 89-96 but especially ROAD 98-106.” Bazzani, paragraph [0342] A ROAD value of 105 is reported for two of the compositions in the Examples relevant to part (c)(Table 23); however, Bazzani does not state that the compositions tested in the relevant Examples either: (a) contained 5 vol.% or more aromatic amine; (b) had a ROAD value of greater than 105; and/or, (c) comprised isoparaffin composition comprising alkylate.
  • Blend 5 the relatively expensive iso-octane and isopentane were replaced with relatively inexpensive alkylate. This embodiment has the advantage of rendering the unleaded fuel composition list costly to produce.
  • a first blend had the following general formula:
  • Example 1 The RON was 116.67, the MON was 106.33, and the octane number was 111.5.
  • the foregoing results demonstrate that the formulas of Example 1 and Example 2 are effective to produce an octane number of 110 or more.
  • a second blend had the following general formula.
  • a third blend had the following general formula.
  • a fourth blend had the following general formula.
  • the numbers in the Table represent the normalized volume %, based on the total volume of the composition, pursuant to ASTM test method D 6730-01, "Standard Test Method for Determination of Individual Components in Spark Ignition Engine Fuels by 100-Metre Capillary (with Precolumn) High-Resolution Gas Chromatography," incorporated herein by reference: Number of carbon atoms Naphthene Iso-paraffins Normal paraffins Aromatics 4 0.36 5 4.07 6 3.79 7 3.93 0.07 8 27.41 54.17 9 1.73 10 0.53 11 0.70 boiling point>200°C 3.24 The RON was 118.5, the MON was 101.9, and the octane number was 110.2.
  • a fifth blend had the following general formula.
  • the numbers in the Table represent volume %, based on the total volume of the composition, pursuant to ASTM test method D 6733-01, "Standard Test Method for Determination of Individual Components in Spark Ignition Engine Fuels by 50-Metre Capillary High-Resolution Gas Chromatography," incorporated herein by reference: Number of carbon atoms Naphthene iso-paraffins normal paraffins aromatics 4 1.01 3.75 5 10.47 0.18 6 0.01 1.27 0.02 7 1.96 8 0.10 73.50 9 0.30 1.80 10 2.41 0.02 11 2.79 The RON was 114, the MON was 105, and the octane number was 110.

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)

Claims (12)

  1. Bleifreie Kraftstoffzusammensetzung, umfassend:
    25 Vol.-% oder mehr alkylierte Benzole, umfassend Alkylgruppen mit 1 bis 4 Kohlenstoffatomen;
    5 Vol.-% oder mehr eines oder mehrerer aromatischer Amine; und,
    eine Isoparaffin-Zusammensetzung, ausgewählt aus Alkylaten und/oder Kombinationen von Isoparaffinen mit einer Gesamtzahl an Kohlenstoffatomen von 11 oder weniger.
  2. Bleifreie Kraftstoffzusammensetzung nach Anspruch 1 mit einer Oktanzahl von mehr als 105.
  3. Bleifreie Kraftstoffzusammensetzung nach Anspruch 1 oder 2 mit einer Oktanzahl von 110 oder mehr.
  4. Bleifreie Kraftstoffzusammensetzung nach einem der Ansprüche 1-3, wobei die Zusammensetzung frei von jedem anderen Bestandteil oder einer Kombination von Bestandteilen ist, die die Oktanzahl der Kraftstoffzusammensetzung um mehr als 1,0 Einheiten erhöht.
  5. Bleifreie Kraftstoffzusammensetzung nach einem der Ansprüche 1-3, ferner umfassend einen oder mehrere sauerstoffhaltige Oktanzahlverbesserer.
  6. Bleifreie Kraftstoffzusammensetzung nach Anspruch 5, wobei der eine oder die mehreren sauerstoffhaltige/n Oktanzahlverbesserer Alkylether, ausgewählt aus der Gruppe bestehend aus Methyl-tertiär-Butylether, Ethyl-tertiär-Butylether und Methyl-tertiär-Amylether, umfassen.
  7. Bleifreie Kraftstoffzusammensetzung nach einem der Ansprüche 1-6, wobei die alkylierten Benzole Alkylgruppen mit 1 bis 2 Kohlenstoffatomen umfassen.
  8. Bleifreie Kraftstoffzusammensetzung nach einem der Ansprüche 1-7, wobei das eine oder die mehreren aromatischen Amine die folgende Struktur aufweisen:
    Figure imgb0006
     wobei R3, R4 und R5 unabhängig voneinander ausgewählt sind aus der Gruppe bestehend aus Wasserstoff und Alkylgruppen mit 1 bis 2 Kohlenstoffatomen.
  9. Bleifreie Kraftstoffzusammensetzung nach Anspruch 8, wobei R3, R4 und R5 unabhängig voneinander ausgewählt sind aus der Gruppe bestehend aus Wasserstoff und Methylgruppen.
  10. Bleifreie Kraftstoffzusammensetzung nach Ansprüchen 8 oder 9, wobei R4 Wasserstoff ist und R5 eine Alkylgruppe ist, die an einer Position relativ zur -HNR3-Gruppe, die aus der Gruppe bestehend aus der meta-Position und der para-Position ausgewählt ist, angeordnet ist.
  11. Bleifreie Kraftstoffzusammensetzung nach einem der Ansprüche 1-10, umfassend:
    im Bereich von 45 bis 50 Vol.-% Isooktan;
    im Bereich von 21 bis 26 Vol.-% Toluol;
    im Bereich von 19 bis 24 Vol.-% m-Xylol;
    im Bereich von 3 bis 7 Vol.-% Isopentan; und
    im Bereich von 5 bis 10 Vol.-% aromatisches Amin.
  12. Bleifreie Kraftstoffzusammensetzung nach einem der Ansprüche 1-11, ferner umfassend:
    40 mg/kg Bleiersatzadditiv;
    30 mg/kg Antioxidans; und,
    von 0,22 bis 0,44 kg/m3 (1 bis 2 g/Gallone) Reinigungsadditiv.
EP06846540.0A 2006-12-11 2006-12-11 Unverbleite kraftstoffzusammensetzungen Active EP2108032B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP12185306A EP2537913A1 (de) 2006-12-11 2006-12-11 Unverbleite Kraftstoffzusammensetzungen

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US2006/061825 WO2008073118A1 (en) 2006-12-11 2006-12-11 Unleaded fuel compositions

Related Child Applications (1)

Application Number Title Priority Date Filing Date
EP12185306A Division-Into EP2537913A1 (de) 2006-12-11 2006-12-11 Unverbleite Kraftstoffzusammensetzungen

Publications (2)

Publication Number Publication Date
EP2108032A1 EP2108032A1 (de) 2009-10-14
EP2108032B1 true EP2108032B1 (de) 2018-09-12

Family

ID=38442290

Family Applications (2)

Application Number Title Priority Date Filing Date
EP06846540.0A Active EP2108032B1 (de) 2006-12-11 2006-12-11 Unverbleite kraftstoffzusammensetzungen
EP12185306A Withdrawn EP2537913A1 (de) 2006-12-11 2006-12-11 Unverbleite Kraftstoffzusammensetzungen

Family Applications After (1)

Application Number Title Priority Date Filing Date
EP12185306A Withdrawn EP2537913A1 (de) 2006-12-11 2006-12-11 Unverbleite Kraftstoffzusammensetzungen

Country Status (4)

Country Link
EP (2) EP2108032B1 (de)
AU (1) AU2006351908B2 (de)
CA (1) CA2672211C (de)
WO (1) WO2008073118A1 (de)

Families Citing this family (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080134571A1 (en) 2006-12-12 2008-06-12 Jorg Landschof Unleaded fuel compositions
US10550347B2 (en) 2009-12-01 2020-02-04 General Aviation Modifications, Inc. High octane unleaded aviation gasoline
US8628594B1 (en) 2009-12-01 2014-01-14 George W. Braly High octane unleaded aviation fuel
US10260016B2 (en) 2009-12-01 2019-04-16 George W. Braly High octane unleaded aviation gasoline
US8324437B2 (en) * 2010-07-28 2012-12-04 Chevron U.S.A. Inc. High octane aviation fuel composition
CA2797163A1 (en) 2011-12-01 2013-06-01 Shell Internationale Research Maatschappij B.V. Balanced unleaded fuel compositions
US9315754B2 (en) 2012-12-27 2016-04-19 Shell Oil Company Compositions
EP2938714A1 (de) 2012-12-27 2015-11-04 Shell Internationale Research Maatschappij B.V. Zusammensetzungen
WO2014172659A1 (en) 2013-04-18 2014-10-23 Swift Fuels, Llc Treating c8-c10 aromatic feed streams to prepare and recover trimethylated benzenes
WO2015023559A1 (en) * 2013-08-12 2015-02-19 Shell Oil Company Methods for modifying auto-ignition properties of a base oil or lubricant composition
US9120991B2 (en) 2013-10-31 2015-09-01 Shell Oil Company High octane unleaded aviation gasoline
RU2665561C2 (ru) * 2013-10-31 2018-08-31 Шелл Интернэшнл Рисерч Маатсхаппий Б.В. Высокооктановый неэтилированный авиационный бензин
ZA201405520B (en) 2013-10-31 2015-09-30 Shell Int Research High octane unleaded aviation gasoline
EP2868734B1 (de) * 2013-10-31 2017-01-11 Shell Internationale Research Maatschappij B.V. Hochoktaniges bleifreies Flugbenzin
GB2515200B (en) * 2013-10-31 2016-03-23 Shell Int Research High octane unleaded aviation gasoline
EA024581B1 (ru) * 2015-04-07 2016-09-30 Джавахар Сингх Октаноповышающая добавка к бензину
WO2018129457A1 (en) 2017-01-06 2018-07-12 Swift Fuels, Llc Treating c8-c10 aromatic feed streams to prepare and recover trimethylated benzenes
US10364399B2 (en) 2017-08-28 2019-07-30 General Aviation Modifications, Inc. High octane unleaded aviation fuel
US10377959B2 (en) 2017-08-28 2019-08-13 General Aviation Modifications, Inc. High octane unleaded aviation fuel
EP4286496A1 (de) * 2022-06-01 2023-12-06 Haltermann Carless Deutschland GmbH Kraftstoffzusammensetzung für kleinmotoren mit spezifischem iso-oktangehalt

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4812146A (en) 1988-06-09 1989-03-14 Union Oil Company Of California Liquid fuels of high octane values
US5284984A (en) * 1992-12-29 1994-02-08 Mobil Oil Corporation Gasoline upgrading by aromatics amination
US5470358A (en) * 1993-05-04 1995-11-28 Exxon Research & Engineering Co. Unleaded aviation gasoline
US7462207B2 (en) 1996-11-18 2008-12-09 Bp Oil International Limited Fuel composition
BRPI0404605B1 (pt) * 2004-10-22 2013-10-15 Formulação de gasolina de aviação
US7740668B2 (en) * 2004-11-30 2010-06-22 Exxonmobil Research & Engineering Company Unleaded aminated aviation gasoline exhibiting control of toluene insoluble deposits

Non-Patent Citations (1)

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

Also Published As

Publication number Publication date
CA2672211A1 (en) 2008-06-19
EP2537913A1 (de) 2012-12-26
WO2008073118A1 (en) 2008-06-19
AU2006351908B2 (en) 2011-03-10
AU2006351908A1 (en) 2008-06-19
CA2672211C (en) 2014-06-10
EP2108032A1 (de) 2009-10-14

Similar Documents

Publication Publication Date Title
US9074153B2 (en) Unleaded fuel compositions
EP2108032B1 (de) Unverbleite kraftstoffzusammensetzungen
US7897034B2 (en) Aviation gasoline formulation
JP4611048B2 (ja) 無鉛高オクタン価ガソリン
JP5147913B2 (ja) 無鉛高オクタン価ガソリンの製造方法
JP5147914B2 (ja) 無鉛ガソリンの製造方法
JP4913448B2 (ja) 無鉛高オクタン価ガソリン
JP5153146B2 (ja) ガソリン組成物
JP4913441B2 (ja) 無鉛ガソリン
JP4913440B2 (ja) 無鉛ガソリン
JP4913433B2 (ja) 無鉛高オクタン価ガソリン
JP4913430B2 (ja) 無鉛高オクタン価ガソリン
JP4913431B2 (ja) 無鉛高オクタン価ガソリン
JP4913432B2 (ja) 無鉛高オクタン価ガソリン
JP4913445B2 (ja) 無鉛高オクタン価ガソリン
JP4913438B2 (ja) 無鉛ガソリン
JP4913439B2 (ja) 無鉛ガソリン
JP4913447B2 (ja) 無鉛高オクタン価ガソリン
JP4913446B2 (ja) 無鉛高オクタン価ガソリン
JP4913429B2 (ja) 無鉛高オクタン価ガソリン
JP2006160922A (ja) ガソリン組成物
JP2003277776A (ja) 燃料油組成物
JP2007246756A (ja) 無鉛高オクタン価ガソリン
JP2007246759A (ja) 無鉛高オクタン価ガソリン
JP2007246757A (ja) 無鉛高オクタン価ガソリン

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

17P Request for examination filed

Effective date: 20090710

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

DAX Request for extension of the european patent (deleted)
17Q First examination report despatched

Effective date: 20100920

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ B.V.

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20180410

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

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 GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK 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: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602006056336

Country of ref document: DE

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1040578

Country of ref document: AT

Kind code of ref document: T

Effective date: 20181015

REG Reference to a national code

Ref country code: NL

Ref legal event code: FP

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: 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: 20180912

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: 20181212

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: 20180912

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: 20181213

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: 20180912

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

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: 20180912

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: 20180912

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1040578

Country of ref document: AT

Kind code of ref document: T

Effective date: 20180912

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: 20180912

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: 20190112

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: 20180912

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: 20180912

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: 20180912

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: 20180912

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: 20180912

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: 20190112

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: 20180912

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602006056336

Country of ref document: DE

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

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: 20180912

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: NL

Ref legal event code: MM

Effective date: 20190101

26N No opposition filed

Effective date: 20190613

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: 20180912

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: 20180912

Ref country code: LU

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

Effective date: 20181211

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: NL

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

Effective date: 20190101

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20181231

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: 20181211

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

Ref country code: BE

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

Effective date: 20181231

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: 20181231

Ref country code: LI

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

Effective date: 20181231

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: 20180912

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: 20061211

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: 20180912

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

Ref country code: FR

Payment date: 20250930

Year of fee payment: 20

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

Ref country code: NL

Payment date: 20251003

Year of fee payment: 20

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

Ref country code: DE

Payment date: 20250930

Year of fee payment: 20

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

Ref country code: GB

Payment date: 20251001

Year of fee payment: 20