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EP1144553B1 - Composition de stabilisation a base d'essence pour prevenir la formation de gomme - Google Patents

Composition de stabilisation a base d'essence pour prevenir la formation de gomme Download PDF

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Publication number
EP1144553B1
EP1144553B1 EP00927725A EP00927725A EP1144553B1 EP 1144553 B1 EP1144553 B1 EP 1144553B1 EP 00927725 A EP00927725 A EP 00927725A EP 00927725 A EP00927725 A EP 00927725A EP 1144553 B1 EP1144553 B1 EP 1144553B1
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EP
European Patent Office
Prior art keywords
gasoline
cracking process
tbc
ppm
pntz
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.)
Expired - Lifetime
Application number
EP00927725A
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German (de)
English (en)
Other versions
EP1144553A3 (fr
EP1144553A2 (fr
Inventor
Andrea Zanotti
Marco Buccolini
Roberto Masciola
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Chimec SpA
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Chimec SpA
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Priority to DK00927725T priority Critical patent/DK1144553T3/da
Publication of EP1144553A2 publication Critical patent/EP1144553A2/fr
Publication of EP1144553A3 publication Critical patent/EP1144553A3/fr
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Publication of EP1144553B1 publication Critical patent/EP1144553B1/fr
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Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • 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
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/16—Hydrocarbons
    • C10L1/1608—Well defined compounds, e.g. hexane, benzene
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
    • C10L1/183—Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • C10L1/224—Amides; Imides carboxylic acid amides, imides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
    • C10L1/2443—Organic compounds containing sulfur, selenium and/or tellurium heterocyclic compounds
    • C10L1/2456—Organic compounds containing sulfur, selenium and/or tellurium heterocyclic compounds sulfur with oxygen and/or nitrogen in the ring, e.g. thiazoles

Definitions

  • the present invention relates to the stabilization of gasoline for preventing gum formation, specifically it relates to gasolines obtained by steam cracking.
  • the stabilizing composition according to the invention is also effective in the stabilization of gasolines outputted from thermal (e.g., Visbreaking, coking and the like), or catalytic (e.g. Fluidized Catalytic Cracking) cracking plants.
  • the stabilization according to the invention is obtained by use of a composition comprising phenothiazine (PNTZ) and tert.butyl catechol, unexpectedly providing, at certain use ratios, a synergistic stabilizing effect.
  • PNTZ phenothiazine
  • tert.butyl catechol tert.butyl catechol
  • gasolines refers to the fuels for the normal internal combustion engines, made of blends of hydrocarbons that may widely differ one from the other according to the production process thereof.
  • the stability issue is particularly critical for those gasolines outputted from cracking plants, containing, in fact, a relatively high amount of hydrocarbons having double bonds readily polymerizable in presence of free radicals (unsaturated hydrocarbons).
  • the stability problem is particularly critical for gasolines produced by a steam cracking process.
  • the problem concerns any thermal (visbreaking, coking, thermal cracking), as well as catalytic (FCC, LC finer, Mild Hydrocracking, HDS) cracked gasoline.
  • the stability is evaluated as resistance to degradation caused by oxygen contact.
  • Effective stabilizers for gasolines of the prior art belong to the class of the aromatic amines.
  • PDA paraphenylenediamines
  • other materials like, e.g., the nitroxides (US-A-5,711,767) or the hindered phenols (US-A-5,509,944).
  • phenotiazine alone or in admixture with other materials, is known to stabilize monomers and as an antifouling agent in oil or petrochemical processes, and overall as a polymerization inhibitor of vinyl aromatic compounds (US-A-4,061,545).
  • the TBC is used in many stabilizing-antifouling agent combinations when an inhibition of polymerization reactions is required, (US-A-3 553 990), and as a retarding agent in the formation of coke and of fouling in petrochemical processes.
  • a gasoline stabilizing composition for inhibiting a gasoline degradation by preventing gum formation in said gasoline, wherein said stabilizing composition comprises as effective inhibition ingredients:
  • a novel solution to the problem of gasolines stabilization and prevention of gum formation is provided by the use of a composition of PNTZ and of TBC in a suitably balanced ratio therebetween, having low toxicity and high effectiveness, equal to or higher than that of the PDA, and void of carcinogenic hazards, in the stabilization of pyrolisis gasolines, particularly of catalytic cracking gasolines.
  • the subject-matter of the present invention is the use of a gasoline stabilizing composition for preventing the gum formation and the degradation thereof, characterized in that it comprises, as effective preventing components, substituted or unsubstituted phenothiazine (PNTZ) or dimer, and tert.butyl-catechol (TBC) in a certain ratio therebetween, as well as the use thereof as a stabilizer, the gasolines thus stabilized and the related gasoline stabilization method.
  • PNTZ substituted or unsubstituted phenothiazine
  • TBC tert.butyl-catechol
  • the gasoline stabilization is carried out by adding to the gasoline 5 to 1000 ppm of a stabilizer, comprising as active stabilizing ingredients PNTZ and TBC in a weight ratio therebetween of 5:95 to 80:20, preferably of 27:75 to 40:60, even more preferably of 30:70 to 35:65, with an optimum value of about 33.3:66.6.
  • a stabilizer comprising as active stabilizing ingredients PNTZ and TBC in a weight ratio therebetween of 5:95 to 80:20, preferably of 27:75 to 40:60, even more preferably of 30:70 to 35:65, with an optimum value of about 33.3:66.6.
  • the dosage of the additive with respect to the gasoline, as well as the ratio of the two compounds, can vary with particular reference to the Bromine number and to the diene value.
  • composition according to the invention may contain, besides the two above-mentioned components, PTNZ and TBC, other PTNZ- and TBC- compatible components and additive carriers commonly used in stabilizing compositions.
  • Particularly suitable solvents are the aromatic solvents, like benzene, toluol and the like, as well as dimethyl-formamide and dimethyl-acetamide.
  • the combined use of the compounds in the blend yields a synergistic effect that is particularly significant at the preferred weight ratio values of the compounds.
  • Stability measurement tests use an assay for measuring the stability to degradation of the gasolines denominated Induction Period (Time?) Method ASTM D525. This method is deemed the most suitable for measuring the stability of the gasolines, by virtue of the predictive capacity thereof of the gum formation due to a gasoline polymerization in presence of oxygen.
  • Such method provides the heating at 100°C (98°C-102°C) of a 50 ml sample in a bomb, sealed and subjected to a 690 kPa (100 psi) air pressure.
  • the test attains a break point, represented by the instant when, on the pressure gauging curve, first a pressure drop of at least 14 kPa (2 psi) over 15 minutes, and then, over the next 15 minutes, another drop of at least 14 kPa (2 psi) take place.
  • the induction time is determined by the time elapsed from the test start (positioning of the bomb inside the heating bath) to the break point.
  • the induction time is a direct expression of the gasoline liability to gum formation during storage. This evaluation parameter is highly significant for highly unstable gasolines, like the cracked ones.
  • TBC tert.butyl-catechol
  • PNTZ phenothiazine
  • the table shows the predictable result that, when used individually, the best products are the PDA and the TBC, in accordance to long-time refinery practice.
  • the blend TBC+PNTZ according to the invention emerges as a stabilizer having an effectiveness even greater than that of the PDA, therefore being capable of replacing the latter with improvement of performance, as well as toxicity elimination.
  • the dosage (quantity in ppm) of the additive according to the invention and of the PDA, the stabilizing effectiveness (induction time) is significantly higher for the blend of the present invention, and this under extremely less critical operative conditions.
  • TBP tert.butyl phenols
  • test results reported in Table 5 should be compared to those of Table 4. They refer to tests carried out in order to simulate a wide range of cracked products, with gasoline characteristics, like, e.g. the Bromine number and the diene value, differing thereamong. This tests prove that the blend PNTZ/TBC of the present invention can replace, even with a higher effectiveness, the PDA+TBP blends, completely avoiding any toxicity hazard deriving from the use of the aromatic amines.
  • the induction time test is applied also in the following examples 5-9, in which the effectiveness of the additive according to the invention (PNTZ-TBC in a 1:2 ratio) is compared to that of other stabilizers of the known art.
  • the test is carried out on gasolines outputted by various industrial FCC (Fluid Catalytic Cracking) plants located in various European countries.
  • the first gasoline sample is made of 26% C5 hydrocarbon cut, 60% light gasoline and 14% medium gasoline. Cut characteristics: Light gasoline Medium gasoline Density 0.680 0.780 P.I. 35°C 71°C 50% vol. 56°C 143°C 95% vol. 110°C 195°C P.F. 139°C 213°C Br N° 92 gr./100 cc 40 gr./100 cc Sulfur 120 ppm 630 ppm Olefins 44% p 27.4% p Paraffins 46.9% p 34.3% p Naphtens 5.4% p 13.5% p Aromatics 3.7% p 24.7% p Blank Induction Time: 75 min.
  • the second gasoline sample has the following characteristics. Cut characteristics: Density 0.678 P.I. 32°C 50% vol. 54°C 95% vol. 106°C P.F. 124°C Br N° 91.5 gr./100 cc Sulfur 96 ppm Olefins 32.5% p Paraffins 58.5% p Naphtenes 6.1% p Aromatics 2.9% p Blank Induction Time: 75 min.
  • the third sample has the following characteristics. Cut characteristics: Density 0.7217 P.I. 35°C 5% vol. 45°C 10% vol. 50°C 30% vol. 62°C 50% vol. 79°C 90% vol. 140°C 95% vol. 150°C P.F. 165°C Sulfur 0.08% p Blank Induction Time: 188 min. Dosage PNTZ + TBC (1:2) PDA + 2,6 DTB Phenol (1:1) 3 ppm 225' 7.5 ppm >520' 9 ppm 207' 22.5 ppm >520'
  • the fourth sample is a light gasoline having the following characteristics. Cut characteristics: Density 0.6638 P.I. 30°C 5% vol. 36°C 50% vol. 51°C 95% vol. 95°C P.F. 144°C Blank Induction Time: 180 min. Dosage PNTZ + TBC (1:2) PDA + 2,6 DTB Phenol (1:1) 15 ppm 870' 45 ppm 555'
  • the fifth sample is a medium gasoline having the following characteristics. Cut characteristics: Density 0.7582 P.I. 87°C 5% vol. 97°C 50% vol. 110°C 95% vol. 139°C P.F. 147°C Blank Induction Time: 90 min. Dosage PNTZ + TBC (1:2) PDA + 2,6 DTB Phenol (1:1) 15 ppm 400' 45 ppm 285'
  • test battery was carried out using a different ASTM test method, always related to the gasoline stability, carried out on a gasoline sample additioned with 100 ppm stabilizer, stored at 40°C for 43 days in a blanketed flask.
  • the so-called existent gums i.e. the quantity of polymers formed (in mg/100 ml gasoline) following a brisk evaporation of a gasoline quantity in a preheated air jet at 160-165 °C, are determined through the ASTM D381/94 method, entitled «Standard test method for existent gum in fuels by Jet Evaporation».

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  • 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)
  • Compositions Of Macromolecular Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)

Claims (21)

  1. Utilisation d'une composition stabilisant l'essence pour inhiber une dégradation de l'essence en évitant la formation de gomme dans ladite essence, dans laquelle ladite composition stabilisante comprend en tant qu'ingrédient efficace d'inhibition :
    A) une phénothiazine (PNTZ) substituée ou non substituée de la formule
    Figure 00230001
    dans laquelle R1 et R2 représentent H, des groupes alkyle en C1 à C20 et des groupes cycloalkyle en C5 à C20, et R3 représente H, des groupes alkyle en C1 à C20 et cycloalkyle en C5 à C20 ou bien phényle, lesdits groupes alkyle et cycloalkyle contenant facultativement des groupes fonctionnels, ou une phénothiazine dimère et
    B) du tert.butyl-catéchol (TBC) de formule
    Figure 00230002
    selon un rapport de 5:95 à 80:20 entre eux.
  2. Utilisation selon la revendication 1, dans laquelle lesdits groupes fonctionnels sont choisis dans la classe comprenant :
    des groupes ester ou acide carboxylique et des dérivés de ceux-ci, du type
    Figure 00240001
    dans laquelle
       R4 est H, OH, R3, -OR1 ou -OR3 ;
       des groupes alcool ou ester du type -O-R3 ;
       des groupes amino du type
    Figure 00240002
    ou des groupes mercaptan ou soufre du type -S-R1.
  3. Utilisation selon la revendication 1 ou 2, dans laquelle ledit rapport est de 27:75 à 40:60.
  4. Utilisation selon l'une quelconque des revendications précédentes, dans laquelle ledit rapport est de 30 :70 à 35 :65.
  5. Utilisation selon l'une quelconque des revendications précédentes, dans laquelle ladite essence est une essence produite par un procédé de craquage.
  6. Utilisation selon la revendication 5, dans laquelle ledit procédé de craquage est un procédé de craquage à la vapeur.
  7. Utilisation selon la revendication 5, dans laquelle ledit procédé de craquage est un procédé de craquage thermique.
  8. Utilisation selon la revendication 5, dans laquelle ledit procédé de craquage est un procédé de craquage catalytique.
  9. Utilisation selon l'une quelconque des revendications précédentes, comprenant en outre des supports habituels compatibles avec PNTZ et TBC.
  10. Essence stabilisée comprenant une essence et une composition stabilisante telle que revendiquée dans l'une quelconque des revendications 1 à 9 en une quantité efficace pour inhiber une dégradation de l'essence en évitant une formation de gomme dans ladite essence.
  11. Essence stabilisée selon la revendication 10, dans laquelle ladite essence est une essence produite par un procédé de craquage.
  12. Essence stabilisée selon la revendication 11, dans laquelle ledit procédé de craquage est un procédé de craquage à la vapeur.
  13. Essence stabilisée selon la revendication 11, dans laquelle ledit procédé de craquage est un procédé de craquage thermique.
  14. Essence stabilisée selon la revendication 11, dans laquelle ledit procédé de craquage est un procédé de craquage catalytique.
  15. Essence stabilisée selon la revendication 10 dans laquelle ladite quantité de composition efficace est de 5 à 1000 ppm.
  16. Essence stabilisée selon l'une quelconque des revendications 10 à 15, dans laquelle le rapport entre la phénothiazine et le tert.butyl-catéchol est de 5:95 à 80:20.
  17. Essence stabilisée selon la revendication 16, dans laquelle ledit rapport est de 27:75 à 40:60.
  18. Essence stabilisée selon la revendication 17, dans laquelle ledit rapport est de 30:70 à 35:65.
  19. Essence stabilisée selon l'une quelconque des revendications 10 à 18, comprenant en outre des additifs et des supports habituels compatibles avec PNTZ et TBC.
  20. Un procédé de stabilisation d'une essence pour inhiber une dégradation de celle-ci en évitant la formation de gomme dans ladite essence, comprenant l'étape d'ajouter à ladite essence une quantité efficace d'une composition stabilisante telle que revendiquée dans la revendication 1.
  21. Procédé pour stabiliser une essence selon la revendication 20, dans lequel ladite quantité efficace est de 5 à 1000 ppm.
EP00927725A 1999-05-07 2000-05-05 Composition de stabilisation a base d'essence pour prevenir la formation de gomme Expired - Lifetime EP1144553B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DK00927725T DK1144553T3 (da) 1999-05-07 2000-05-05 Benzinstabiliserende sammensætning til forhindring af gummidannelse

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
ITRM990286 1999-05-07
IT1999RM000286A IT1306138B1 (it) 1999-05-07 1999-05-07 Composizione stabilizzante per benzine per inibire la formazione digomme.
PCT/IT2000/000175 WO2000068343A2 (fr) 1999-05-07 2000-05-05 Composition de stabilisation a base d'essence pour prevenir la formation de gomme

Publications (3)

Publication Number Publication Date
EP1144553A2 EP1144553A2 (fr) 2001-10-17
EP1144553A3 EP1144553A3 (fr) 2002-09-11
EP1144553B1 true EP1144553B1 (fr) 2004-10-20

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EP00927725A Expired - Lifetime EP1144553B1 (fr) 1999-05-07 2000-05-05 Composition de stabilisation a base d'essence pour prevenir la formation de gomme

Country Status (10)

Country Link
EP (1) EP1144553B1 (fr)
AT (1) ATE280211T1 (fr)
AU (1) AU4611000A (fr)
DE (1) DE60015073T2 (fr)
DK (1) DK1144553T3 (fr)
ES (1) ES2231192T3 (fr)
IT (1) IT1306138B1 (fr)
NO (1) NO20010051L (fr)
PT (1) PT1144553E (fr)
WO (1) WO2000068343A2 (fr)

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2006756A (en) * 1932-04-04 1935-07-02 Rubber Service Lab Co Liquid fuel composition
GB595916A (en) * 1944-10-18 1947-12-23 Kodak Ltd Improvements in motor fuels
DE1034919B (de) * 1957-06-26 1958-07-24 Gelsenberg Benzin Ag Zusatz zu Kraftstoffen
US3031281A (en) * 1957-10-31 1962-04-24 Goodyear Tire & Rubber Antioxidants in gasoline fuels
US3102871A (en) * 1961-05-01 1963-09-03 Goodyear Tire & Rubber Antioxidants
US3839210A (en) * 1971-12-01 1974-10-01 Gaf Corp Antioxidant composition comprising a synergistic mixture of a phenol, amine and sulfone
US4061545A (en) * 1976-02-19 1977-12-06 Cosden Technology, Inc. Polymerization inhibitor for vinyl aromatic compounds
US4177110A (en) * 1978-07-18 1979-12-04 Cosden Technology, Inc. Method for the distillation of vinyl aromatic compounds using polymerization inhibitors with low-volatility
US4466904A (en) * 1983-01-10 1984-08-21 Cosden Technology, Inc. Polymerization co-inhibitors for vinyl aromatic compounds
US4511457A (en) * 1984-08-10 1985-04-16 Atlantic Richfield Company Method for minimizing fouling of heat exchanger
US4785095A (en) * 1986-09-16 1988-11-15 The Lubrizol Corporation N-substituted thio alkyl phenothiazines

Also Published As

Publication number Publication date
WO2000068343A3 (fr) 2001-08-16
DK1144553T3 (da) 2005-01-31
EP1144553A3 (fr) 2002-09-11
PT1144553E (pt) 2005-02-28
ITRM990286A1 (it) 2000-11-07
NO20010051L (no) 2001-03-07
IT1306138B1 (it) 2001-05-30
ATE280211T1 (de) 2004-11-15
AU4611000A (en) 2000-11-21
ES2231192T3 (es) 2005-05-16
NO20010051D0 (no) 2001-01-04
DE60015073T2 (de) 2006-02-02
WO2000068343A2 (fr) 2000-11-16
EP1144553A2 (fr) 2001-10-17
DE60015073D1 (de) 2004-11-25

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