EP1657290B1 - Procédé de production d'essence à partir du gaz de synthèse comprenant une étape de régénération de catalyseur - Google Patents

Procédé de production d'essence à partir du gaz de synthèse comprenant une étape de régénération de catalyseur Download PDF

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Publication number
EP1657290B1
EP1657290B1 EP20040105668 EP04105668A EP1657290B1 EP 1657290 B1 EP1657290 B1 EP 1657290B1 EP 20040105668 EP20040105668 EP 20040105668 EP 04105668 A EP04105668 A EP 04105668A EP 1657290 B1 EP1657290 B1 EP 1657290B1
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European Patent Office
Prior art keywords
catalyst
process according
regeneration
zeolite
percent
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EP20040105668
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German (de)
English (en)
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EP1657290A1 (fr
Inventor
Yahya 3rd Floor No.16 Kalantary Zamani
Ali Nakhaei First Floor No.4 Khoshnevisan Pour
Kheirollah Jafari Jozani
Jafar Yeganeh Mehr
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Research Institute of Petroleum Industry
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Research Institute of Petroleum Industry
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
    • C10G2/334—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing molecular sieve catalysts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
    • C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
    • C10G2/332—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the iron-group

Definitions

  • the present invention relates to a new and advantageous single-stage Gasoline production process from syngas.
  • the catalyst can be regenerated in an easy manner without stopping the process.
  • Such a process is more economic and still further leads to constant octane numbers of the product at values of about 95.
  • the new process prevents the catalyst from deactivation and increases its capacity, resulting in better conversion rates, becoming even better after each regeneration step. Also, with the process according to the invention the catalyst's lifetime is significantly prolonged, making the whole process more economic.
  • the Fischer-Tropsch (FT) process was first commercially applied in 1930, in Germany, where, using a cobalt catalyst together with a promoter in a fixed bed reactor, more than (1,590,000 liters (10,000 barrels) of hydrocarbons were daily produced.
  • US 3,958,957 reports about regeneration of a catalyst through oxidation by air.
  • US 4,151,190 refers to a method for regenerating a catalyst by hydrogen gas at 500 to 600°C, applying a process that takes 16 hours of time.
  • the catalyst used according to US 4,738,948 contains Co and Ru and was regenerated by hydrogen gas at temperatures between 150 to 300 °C.
  • US 5,728,918 describes a method for regenerating a cobalt based catalyst comprising a support, which is used to synthesize C 5 + hydrocarbons.
  • This method includes the application of carbon monoxide and 30 percent of hydrogen gas at a temperature which is 10°C higher than the one usually used during FT process (that is 220 to 230 °C), under pressure of from 0.5 to 10 bars for 1 to 15 hours.
  • the cobalt based catalyst used in the FT process described in the US 4,595,703 was regenerated by making use of hydrogen gas in the presence of nitrogen, carbon monoxide and methane gas at the same temperature as the reaction temperature.
  • US 4,622,308 discloses a catalyst for use in Fischer-Tropsch process comprising iron, a zeolite and at least one metal selected from the group consisting of ruthenium, rhodium, platinum, palladium, iridium, cobalt and molybdenum. This document does not suggest any process for the regeneration of Fischer-Tropsch catalysts.
  • EP 0 418 048 A1 discloses a catalyst composition for conversion of syngas to a mixture of hydrocarbons with elevated aromaticity.
  • the catalyst compositions described therein comprise either cobalt or iron and a zeolite. Additionally, this document discloses a plurality of possible further ingredients to the catalyst, one of them is copper.
  • the catalyst according to this disclosure comprises a zeolite that has a silicator alumina ratio of 60. No regeneration processes during Fischer-Tropsch synthesis are mentioned in this document.
  • US 4,207,208 refers to a Fischer-Tropsch process comprising four steps in sequence, wherein the catalyst is oxidized in the first step, reduced in hydrogen in a second step, again oxidized in a third step and again reduced in a fourth step, the fourth step comprising treatment of the catalyst with syngas.
  • the catalyst used in this document is quite special as it comprises water insoluble organic iron compounds.
  • US 6,022,755 refers to a regeneration process of Fischer-Tropsch catalysts during operation of the system by reducing the space velocity of the feed. This document suggests reducing the space velocity to such an extent that the H 2 /CO ratio of the exit gas is exceeding 10:1.
  • the catalyst used in this process is a cobalt catalyst.
  • the regeneration process of a catalyst depends on multiple factors, such as operation conditions of the reactor type, the structure of the catalyst, the type of end products and the reduction and activation conditions for the particular catalyst. As a result, finding a suitable regeneration process differs from case to case, even if with a similar process only operation conditions are changed.
  • Regeneration includes the elimination of the sediment coke built on the surface of the catalyst by hydrogenation and/or combustion with oxygen. For such regeneration processes, the whole FT process has to be stopped and then resumed after the regeneration step.
  • a catalyst based on iron compounds as catalytically active species comprising further Zeolite components shows superior qualities during FT synthesis processes, in particular as to superior possibilities for its regeneration.
  • the whole FT can be run continuously without any interruption for catalyst regeneration.
  • the whole process, including the regeneration process of the catalyst can be furthermore improved with adopting particular process parameter, such as the space velocity, which makes an easy regeneration of the catalyst possible while continuously running the process.
  • the deactivation of the catalyst is to be regarded in connection with the following parameters:
  • sedimentation of carbon compounds on the active sites of the iron - Zeolite catalyst leads to deactivation.
  • the decomposition of methane is endothermic while the disproportionation of CO is exothermic. So, by increasing the temperature, the methane decomposition increases, while the disproportionation of CO declines.
  • Another aspect when regarding the activity of a catalyst in a FT process is the coverage of the Zeolite components present in the system, as a result of which the active acidic sites are hidden from the reactants and don't take part in the overall reaction.
  • the new and advantageous process making use of a catalyst as described in independent Claim 1, which catalyst is suited for regeneration while the process is running leads to significant and up to two times longer life times of the Fe-Zeolite catalyst while the whole FT process runs without interruption and with a constant selectivity of the catalyst throughput.
  • the zeolite within the catalyst has a pore size of more than 5 ⁇ .
  • the catalyst used in the process according to the present invention preferably comprises silicon oxides.
  • the amounts of copper oxide preferably range from 3 to 10 percent by weight, preferably the amount of potassium oxide ranges from 1 to 3 percent by weight, preferably the amount of silicon oxide ranges from 15 to 25 percent by weight.
  • the catalyst used within the process according to the present invention is in the form of cylindrical pellets having a diameter of from 3 to mm and a height of from 3 to 7 mm.
  • the Fe catalyst is prepared by the co- precipitation of a solution of respective cations Fe2+, Fe3+ and Cu2+ with a bicarbonate or sodium carbonate solution.
  • the solutions of the cations are prepared by completely dissolving 0.035 to 0.095 mole (of copper nitrate, 0.1 to 0.8 mole of Fe (III) chloride, a solution of 0.6 to 1.5 mole of Fe (II) chloride per litre of water, in such a way that the total amount of cations per litre of the solution is not less that 0.4 mole, and more than 0.6 mole.
  • the solutions of the cations were prepared in amounts of between 2 to 10 and preferably of between 4 to 6 litres.
  • the precipitating solution is prepared by dissolving sodium bicarbonate or sodium carbonate in an amount of 200 to 400 grams, equivalent to the solutions of the cations, in deionised water. Both solutions are heated up to 60 to 80 °C, and are then added to the precipitation system that contains 100 to 1000 millilitres of deionised water, that is heated up to the same temperature used for the ionic solutions. The rate of the addition of the solutions to the precipitation system is controlled such that the pH value of the solution remains between 5 to9. The precipitates are filtrated off and washed with deionised water for several times to eliminate all the remaining cations and anions.
  • the alkaline salt and surface area modifiers potassium silicate together with a silica-sol solution is added to the resulting cake.
  • the amount of potassium oxide has to be between 1 to 3 percent by weight and that the percentage of silicon dioxide should not exceed 15 to 25 percents by weight, based on the amount of iron present.
  • the resulting catalyst is dried at a temperature of from 100 to 150 °C for 12 to 30 minutes and is calcinated at 400 to 500 °C in an air flow, for 4 to 8 hours.
  • the atomic ratio of iron of the resulting catalyst is calculated based on the formula a [M/(M+Fe)] x 100 (where M represents all metal oxides).
  • the atomic ratios of the resulting iron catalyst is as follows: 100Fe / 3-10Cu0 / 0.5-3K 2 O / 15-25 SiO 2
  • the Zeolite is mixed with the iron catalyst: the Zeolite part of the catalyst is an HZSM5 with a silica to alumina ratio between 12 to 40.
  • the proposed catalyst is composed of a physical mixture of the iron catalyst with the Zeolithe, prepared from the mentioned Zeolite with using a molecular sieve having a mesh of 100 to 150, to homogenize the size.
  • the weight percent of the final Fe- Zeolite catalyst is composed of from 10 to 30 percent of iron and from 70 to 90 percent of the Zeolite.
  • an appropriate adhesive agent having a good thermal and mechanical as well as abrasion resistance is formed, which adhesive agent does not have any negative effect on the selectivity of the desired end products and the activity of the catalyst.
  • Alumina, silica and silica - alumina gels were used for this purpose, in total weight percents of from 10 to 30.
  • the alumina gel was prepared by dissolving respective aluminium salts in deionised water and precipitating them with ammonium salts.
  • the silica gel was prepared by precipitating a silica sol solution with nitric acid, and a alumina-silica gel was produced by dissolving aluminium salts in a silica sol solution and precipitation by adjusting the pH at values of between 5 to 9.
  • the iron catalyst was prepared from aqueous salt solution of contain Fe2+, Fe3+ and Cu2+ with sodium carbonate solution, using the co-precipitation method.
  • the mixture of cations was prepared by dissolving exactly 0.035 to 0.095 mole of copper nitrate, 0.60 to 1.50 mole of iron (III) chloride and 0.10 to 0.80 mole of iron (II) chloride in one liter of total solution.
  • the precipitating solution was prepared by dissolving sodium bicarbonate or carbonate in an amount of 200 to 400 grams, in a volume of deionized water, equivalent to those of the cation solutions. Bath solution were heated up to 60 to 80 °C and added to a precipitation system containing 100 to 1000 ml of equivalently heated deionized water. The addition rate was adjusted in a way that the pH of the solution remained in the range of 4 to 10.
  • the precipitates were filtered and washed thoroughly with deionized water for several times in order to remove the excess cations and anions.
  • a suitable amount of potassium silicate and silica sol was added to the formed cake, in a way that the amount of potassium and silicon oxides do not exceed 1 to 3 and 15 to 25 percents by weight respectively.
  • the formed catalyst was heated in 100 to 150 °C for 12 to 30 hours and was calcinated in 400 to 500 °C in an air flow for 4 to 8 hours.
  • the atomic ratio of the formed catalyst with respect to iron was calculated using the [M/(M+Fe)] x 100 formulas where M represents metal oxide the atomic ratios for the prepared catalyst are: 100 Fe/3-10 CuO/0.5 - 3 K 2 O / 15-25 SiO 2
  • HZSM5 catalyst with a silicon to Alumina ratio of 12-40 was prepared, using the method disclosed in the Egyptian patent No. 25 845 .
  • the catalyst according to the invention was prepared by physically mixing the prepared iron catalyst with HZSM5 Zeolite. A sieve with mesh size of 100 to 150 was used for adjusting the size.
  • the catalyst was prepared in such a way that the eight percent of iron were present and between 10 to 30 and 70 to 90 weight percents of the catalyst are zeolite.
  • a suitable binder is one of the important features.
  • the silica gel was prepared by precipitation of silica sol by nitric acid and the silica-alumina gel was prepared by dissolving aluminium salts in a silica sol and then precipitation by controlled pH in a range of 6 to 8.
  • oxidation and reduction method oxygen or air is used for burning hydrocarbons or coke remaining in or onto the catalyst.
  • the reduction method the heavy hydrocarbons remaining on the catalyst as well as the coke placed on the active sites of the catalyst are converted to methane in a process called methanation making use of hydrogen.
  • a water - gas shift reaction is observed in addition to the main process, which is caused by the absorption of carbon monoxide on the catalyst surface, the formation of surface carbides and chain growth.
  • a water - gas shift reaction includes the reaction of carbon monoxide with water and the formation of carbon dioxide and hydrogen. This reaction is shown below: CO + H 2 O C0 2 + H 2
  • hydrogen gas is produced during the water - gas shift reaction.
  • This produced hydrogen can be used to regenerate the catalyst.
  • the occurrence of the water-gas shift reaction among the total reactions is increased.
  • Such an effect can be achieved by decreasing the space rate of the feed to 20 to 70 percents (based on the total volume of the reaction) and hence 90-99 percents of carbon monoxide is converted to hydrogen through the water-gas shift reaction.
  • This provides enough hydrogen to regenerate the catalyst.
  • the process to regenerate the catalyst by the produced hydrogen is performed at temperatures of the catalyst bed of between 280 to 300°C and under a pressure of 10 to 30 bars, after every 120 to 200 hours of the running process.
  • the iron catalysts according to the invention can successfully be regenerated by such a process without any need to stop the process, i.e. the regeneration process can be achieved with simultaneously running the main process.
  • the Fe-Cu - k catalyst was prepared by coprecipitation of iron and copper salts (Iron nitrates and copper nitrates), under controlled pH and temperature, with a final addition of potassium oxide.
  • the prepared Fe catalyst was then physically mixed with the commercial HZSM5 Zeolite () by addition of silica - alumina gel (with a ratio of 70 to 10 percents of silica, and 30 to 90 percents of alumina) as an adhesive agent (in an amount of 10 to 15 weight%).
  • the catalyst was formed to cylindrical pills with a diameter of about 4 mm and a length of 3 mm making use of a tableting press.
  • the final catalyst was calcinated in airflow, at 450 °C.
  • the activity of the catalyst was tested in a fixed-bed steel reactor of 2cm in diameter, which was furnished with a thermowall and a thermo couple.
  • the flow of feed is controlled by mass - flow meters.
  • the heating system consists of electrical heating jackets, each of which is controlled by a temperature controller.
  • the temperature of the reactor outlet that passes through a pressurized container to collect the yielded liquid is lowered with a cooling system.
  • the catalyst was moved to a reactor and finally prepared by reduction and carbonization stages. In the reduction stage, the catalyst stayed in a flow of nitrogen containing 5 to 8 percents by volume of hydrogen with a space rate of from 10 to 20 liters (g.Fe.h) -1 and was heated up to 250-270°C, with a temperature gradient of 10 °C /min.
  • the regeneration by reduction of feed rate process was quickly performed, while the reaction was in process, after every 120 to 200 hours. During each regeneration reaction, the space velocity of the feed was reduced to 20, 45 and 70 percents of its initial values. As mentioned before, the initial values are 2 to 4 liters (g.Fe.h) -1 .
  • the reaction was performed for 641 successive hours, during which the octane number of the product remained constant at about 95. Running the process under such conditions did not only prevent the catalyst from deactivation but also the capacity of the catalyst was increased, resulting in better conversion rates, becoming even better after each recycling step.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (12)

  1. Procédé de production d'essence à partir d'un gaz de synthèse, dans lequel un catalyseur est mis en contact avec un gaz de synthèse et le catalyseur comprend de l'oxyde de fer, une zéolithe, un liant et un oxyde métallique comprenant l'oxyde de cuivre et/ou l'oxyde de potassium, caractérisé en ce que le procédé comprend en outre l'étape de régénération du catalyseur à l'intérieur du réacteur en diminuant la vitesse spatiale de l'alimentation de 20 à 70 pour cent par rapport à la vitesse initiale à une température située entre 280 °C et 300 °C et à une pression située entre 10 bar et 30 bar.
  2. Procédé selon la revendication 1, dans lequel le procédé de régénération est répété après 120 à 200 heures de fonctionnement.
  3. Procédé selon la revendication 1, dans lequel le liant est un gel de silice-alumine.
  4. Procédé selon la revendication 1, dans lequel la zéolithe à l'intérieur du catalyseur est une zéolithe présentant un rapport silice/alumine allant de 12 à 40.
  5. Procédé selon la revendication 1, dans lequel la zéolithe possède une taille de pore supérieure à 5 Å.
  6. Procédé selon la revendication 1, dans lequel la zéolithe est H-ZSM5.
  7. Procédé selon la revendication 6, dans lequel le catalyseur comprend 70 à 90 pour cent en poids de H-ZSM5.
  8. Procédé selon la revendication 1, dans lequel le catalyseur utilisé comprend des oxydes de silicium.
  9. Procédé selon la revendication 1, dans lequel la quantité d'oxyde de cuivre est située dans la plage allant de 3 à 10 pour cent en poids.
  10. Procédé selon la revendication 1, dans lequel la quantité d'oxyde de potassium est située dans la plage allant de 1 à 3 pour cent en poids.
  11. Procédé selon la revendication 8, dans lequel la quantité d'oxyde de silicium est située dans la plage allant de 15 à 25 pour cent en poids.
  12. Procédé selon la revendication 1, dans lequel le catalyseur est sous la forme de granulés cylindriques possédant un diamètre allant de 3 mm à 6 mm et une hauteur allant de 3 mm à 7 mm.
EP20040105668 2004-11-10 2004-11-10 Procédé de production d'essence à partir du gaz de synthèse comprenant une étape de régénération de catalyseur Expired - Fee Related EP1657290B1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
DE200460027388 DE602004027388D1 (de) 2004-11-10 2004-11-10 Verfahren zur Herstellung von Benzin aus Synthesegas mit einem Schritt der Regeneration von Katalysator
EP20040105668 EP1657290B1 (fr) 2004-11-10 2004-11-10 Procédé de production d'essence à partir du gaz de synthèse comprenant une étape de régénération de catalyseur

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EP20040105668 EP1657290B1 (fr) 2004-11-10 2004-11-10 Procédé de production d'essence à partir du gaz de synthèse comprenant une étape de régénération de catalyseur

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EP1657290A1 EP1657290A1 (fr) 2006-05-17
EP1657290B1 true EP1657290B1 (fr) 2010-05-26

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2009316748B2 (en) * 2008-11-18 2013-12-19 Res Usa, Llc Method for activating strengthened iron catalyst for slurry reactors

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10086365B2 (en) 2007-08-30 2018-10-02 Res Usa, Llc Strengthened iron catalyst for slurry reactors
CN102105220A (zh) * 2008-06-02 2011-06-22 瑞恩泰克公司 通过铁硝酸盐和沉淀剂共进料或从硝酸亚铁溶液和硝酸铁溶液分别沉淀来强化铁费-托催化剂
US7943674B1 (en) 2009-11-20 2011-05-17 Chevron U.S.A. Inc. Zeolite supported cobalt hybrid fischer-tropsch catalyst
US8445550B2 (en) 2010-11-23 2013-05-21 Chevron U.S.A. Inc. Ruthenium hybrid fischer-tropsch catalyst, and methods for preparation and use thereof
US20130158138A1 (en) * 2011-12-15 2013-06-20 Chevron U.S.A. Inc. Integral synthesis gas conversion catalyst extrudates and methods for preparing and using same
WO2013093423A1 (fr) * 2011-12-19 2013-06-27 Compactgtl Limited Procédé de régénération d'un catalyseur de fischer-tropsch
WO2013093428A1 (fr) * 2011-12-19 2013-06-27 Compactgtl Limited Fonctionnement d'un procédé catalytique fischer-tropsch
US10589257B2 (en) 2015-04-07 2020-03-17 B.G. Negev Technologies And Applications Ltd., At Ben-Gurion University Catalyst composition and catalytic processes for producing liquid hydrocarbons
CN107999084B (zh) * 2016-11-01 2020-09-29 神华集团有限责任公司 一种低温耐硫变换催化剂及其制备方法
JP2020081958A (ja) * 2018-11-22 2020-06-04 ダイキン工業株式会社 ペレット及び反応器

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DE731295C (de) 1936-08-02 1943-02-05 Studien Und Verwertungs G M B Verfahren zur Herstellung von Paraffin aus Kohlenoxyd und Wasserstoff
US2540109A (en) * 1946-05-15 1951-02-06 Phillips Petroleum Co Process for reactivating catalysts
US4207208A (en) * 1978-12-18 1980-06-10 Mobil Oil Corporation Method for regeneration and activity improvement of syngas conversion catalyst
CA1176228A (fr) * 1981-05-18 1984-10-16 Minoru Koikeda Catalyseur pour la preparation d'hydrocarbures a partir de gaz de synthese
FR2556237B1 (fr) * 1983-12-07 1986-09-19 Raffinage Cie Francaise Nouvelle composition catalytique et application a la conversion de gaz de synthese en un melange d'hydrocarbures a aromaticite elevee
GB2299767B (en) * 1995-04-07 1998-05-13 Norske Stats Oljeselskap Regneration of fischer-tropsch catalysts

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2009316748B2 (en) * 2008-11-18 2013-12-19 Res Usa, Llc Method for activating strengthened iron catalyst for slurry reactors

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EP1657290A1 (fr) 2006-05-17

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