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EP1613912B1 - Method for suddenly cooling high-temperature gas - Google Patents

Method for suddenly cooling high-temperature gas Download PDF

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Publication number
EP1613912B1
EP1613912B1 EP04714282A EP04714282A EP1613912B1 EP 1613912 B1 EP1613912 B1 EP 1613912B1 EP 04714282 A EP04714282 A EP 04714282A EP 04714282 A EP04714282 A EP 04714282A EP 1613912 B1 EP1613912 B1 EP 1613912B1
Authority
EP
European Patent Office
Prior art keywords
cooling
gas stream
quench
area
water
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
EP04714282A
Other languages
German (de)
French (fr)
Other versions
EP1613912A1 (en
Inventor
Günter H. KISS
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.)
Thermoselect AG
Original Assignee
Thermoselect AG
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 Thermoselect AG filed Critical Thermoselect AG
Priority to SI200431190T priority Critical patent/SI1613912T1/en
Publication of EP1613912A1 publication Critical patent/EP1613912A1/en
Application granted granted Critical
Publication of EP1613912B1 publication Critical patent/EP1613912B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28C—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA COME INTO DIRECT CONTACT WITHOUT CHEMICAL INTERACTION
    • F28C3/00—Other direct-contact heat-exchange apparatus
    • F28C3/06—Other direct-contact heat-exchange apparatus the heat-exchange media being a liquid and a gas or vapour
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/04—Purifying combustible gases containing carbon monoxide by cooling to condense non-gaseous materials
    • C10K1/06—Purifying combustible gases containing carbon monoxide by cooling to condense non-gaseous materials combined with spraying with water
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28C—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA COME INTO DIRECT CONTACT WITHOUT CHEMICAL INTERACTION
    • F28C3/00—Other direct-contact heat-exchange apparatus
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28C—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA COME INTO DIRECT CONTACT WITHOUT CHEMICAL INTERACTION
    • F28C3/00—Other direct-contact heat-exchange apparatus
    • F28C3/06—Other direct-contact heat-exchange apparatus the heat-exchange media being a liquid and a gas or vapour
    • F28C3/08—Other direct-contact heat-exchange apparatus the heat-exchange media being a liquid and a gas or vapour with change of state, e.g. absorption, evaporation, condensation
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
    • F28D21/00—Heat-exchange apparatus not covered by any of the groups F28D1/00 - F28D20/00
    • F28D2021/0019—Other heat exchangers for particular applications; Heat exchange systems not otherwise provided for
    • F28D2021/0075—Other heat exchangers for particular applications; Heat exchange systems not otherwise provided for for syngas or cracked gas cooling systems

Definitions

  • the present invention relates to the shock-cooling of high-temperature gases according to a device according to claim 1 and a method according to claim 5. Furthermore, the invention relates to the use of the device according to the invention and the method according to the invention in a high-temperature recycling method according to claim 11.
  • quench In high-temperature process technology, flue gases are rapidly cooled by the addition of liquids such as water in a variety of applications. This is called the process of quenching, the apparatus used for this is the so-called quench.
  • the water is circulated by means of quench pumps. Between water inlet and outlet, the quench water heats up by approx. 10 to 30 ° C. This heat energy is removed by quench heat exchanger from the system.
  • Characteristic of the process is that in addition to the cooling of the gas and foreign substances in the gas are deposited in the liquid. Contamination of the heat exchangers, the pipelines and all quench water-conducting apparatus is unavoidable. Therefore, repeated cleaning is necessary.
  • the object of the invention is to provide a device and a method in which on the one hand, the cooling of the gases can be done with high efficiency, and on the other hand, the cleaning work can be reduced to a minimum. Furthermore, the object of the present invention is to specify a use of such a device and such a method.
  • Circuit 1 serves for the actual shock-cooling of the high-temperature gas in a first region along the flow direction of the gas, in which case also the solid particles contained in the gas are separated
  • - Circuit 2 serves for the final cooling in a second region along the flow direction of the gas to the final temperature.
  • the advantageous effect of the invention is the localization of the solid particles precipitated by the shock cooling in a limited range of cooling. In connection with the embodiment mentioned below, even the complete avoidance of contamination of heat exchangers by the separated, solid particles is possible.
  • the quench heat exchangers are arranged exclusively in the clean circuit 2. About this Quenchowskiargueser the energy contained in the high-temperature gas is dissipated. Consequently, the circuit 1, d. i. the actual quench circuit, without heat exchanger. Contamination of the first cooling circuit is thus largely excluded.
  • the quench device is a slender apparatus with a concentrically arranged inner tube, wherein the hot gas From above into the inner tube enters and flows through the apparatus from top to bottom. In the lower area, the gas is deflected by a deflection device, then flows through the outer annular gap upwards and leaves the apparatus at the upper end.
  • the cooling in the inner tube is preferably carried out from 1000 ° C to 2000 ° C to 95 ° C to 70 ° C, more preferably 85 ° C, and in the outer annular gap of 85 ° C to 70 to 40, preferably 60 ° C.
  • quench water is discharged via a free overflow from the circuit 2 in the circuit 1.
  • the level control of the two quench water levels existing in the circuit 1 and circuit 2 takes place via the quench water level in the circuit 1.
  • the mechanism of the level control is preferably realized by the supply or removal of water from the circuit 1.
  • flue gases having temperatures of 1000 ° C. to 2000 ° C., preferably 1200 ° C. are preferably shock-cooled.
  • the quenching leads the high-temperature gas of more than 1200 ° C to 95 ° C to 70 ° C, preferably 85 ° C in the first, preferably consisting of an inner tube area.
  • the process is preferably carried out for waste gases having a water content of 10% by volume to 70% by volume, particularly preferably 30% by volume.

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Heat-Exchange Devices With Radiators And Conduit Assemblies (AREA)
  • Heat Treatment Of Articles (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Heat Treatment Of Strip Materials And Filament Materials (AREA)
  • Industrial Gases (AREA)
  • Waste-Gas Treatment And Other Accessory Devices For Furnaces (AREA)
  • Furnace Details (AREA)

Abstract

The invention relates to a quench device for suddenly cooling a hot gas stream with the aid of quench water. The inventive quench device comprises a gas supply line and a gas drainage pipe. Said quench water is at least partially cooled by means of a heat exchanger. In addition, said quench device is provided with a cooling water circuit for cooling the first area of the gas stream and with a second separate cooling circuit which cools a second area of the gas stream and is arranged downstream.

Description

Die vorliegende Erfindung beschäftigt sich mit der Schockkühlung von Hochtemperaturgasen entsprechend einer Vorrichtung nach Patentanspruch 1 und eines Verfahrens nach Anspruch 5. Desweiteren betrifft die Erfindung die Verwendung der erfindungsgemäßen Vorrichtung und des erfindungsgemäßen Verfahren in einem Hochtemperaturrecyclingverfahren nach Anspruch 11.The present invention relates to the shock-cooling of high-temperature gases according to a device according to claim 1 and a method according to claim 5. Furthermore, the invention relates to the use of the device according to the invention and the method according to the invention in a high-temperature recycling method according to claim 11.

In der Hochtemperaturverfahrenstechnik werden bei einer Vielzahl von Anwendungsfällen Rauchgase durch Zugabe von Flüssigkeiten wie zum Beispiel Wasser schockartig abgekühlt. Man spricht hierbei vom Vorgang des Quenchens, der dafür genutzte Apparat ist die sogenannte Quench.
Das Wasser wird mittels Quenchpumpen im Kreislauf geführt. Zwischen Wassereintritt und Austritt erwärmt sich das Quenchwasser um ca. 10 bis 30 °C. Diese Wärmeenergie wird mittels Quenchwärmetauscher aus dem System abgeführt.
Charakteristisch für den Prozess ist, dass neben der Abkühlung des Gases auch im Gas befindliche Fremdstoffe in der Flüssigkeit abgeschieden werden. Eine Verschmutzung der Wärmetauscher, der Rohrleitungen sowie aller quenchwasserführenden Apparate ist nicht vermeidbar. Deshalb ist eine wiederholte Reinigung notwendig.In high-temperature process technology, flue gases are rapidly cooled by the addition of liquids such as water in a variety of applications. This is called the process of quenching, the apparatus used for this is the so-called quench.
The water is circulated by means of quench pumps. Between water inlet and outlet, the quench water heats up by approx. 10 to 30 ° C. This heat energy is removed by quench heat exchanger from the system.
Characteristic of the process is that in addition to the cooling of the gas and foreign substances in the gas are deposited in the liquid. Contamination of the heat exchangers, the pipelines and all quench water-conducting apparatus is unavoidable. Therefore, repeated cleaning is necessary.

In der DE 24 16 167 A1 ist eine Vorrichtung zum Kühlen heißer und feuchter Gase, in der DE 100 04 138 A1 eine 2-stufige Synthesegaskühlung beschrieben. Letztlich beschreibt die DE 196 33 830 C2 eine Kühlvorrichtung.In the DE 24 16 167 A1 is a device for cooling hot and humid gases, in the DE 100 04 138 A1 a 2-stage synthesis gas cooling described. Ultimately, that describes DE 196 33 830 C2 a cooling device.

Aufgabe der Erfindung ist es, eine Vorrichtung und ein Verfahren anzugeben, bei dem zum einen die Abkühlung der Gase mit hoher Effizienz erfolgen kann, und zum anderen die Reinigungsarbeiten auf ein Mindestmass reduziert werden können. Des Weiteren ist der Ziel der vorliegenden Erfindung eine Verwendung einer solchen Vorrichtung und eines solchen Verfahrens anzugeben.The object of the invention is to provide a device and a method in which on the one hand, the cooling of the gases can be done with high efficiency, and on the other hand, the cleaning work can be reduced to a minimum. Furthermore, the object of the present invention is to specify a use of such a device and such a method.

Diese Aufgabe wird erfindungsgemäß durch eine Vorrichtung gemäß Patentanspruch 1, ein Verfahren gemäß Patentanspruch 5 und durch eine Verwendung gemäß Patentanspruch 11 gelöst.This object is achieved by a device according to claim 1, a method according to claim 5 and by a use according to claim 11.

Demnach wird zur erfindungsgemäßen Lösung der Aufgabe der Schockkühlung des Hochtemperaturgases, die Entwicklung einer Zweistufen-Quench vorgeschlagen. In zwei entlang der Strömungsrichtung des Hochtemperaturgases nacheinander lokalisierte Stufen bzw. Bereiche des Hochtemperaturgasstromes wird die Kühlung über zwei separate Kühlkreisläufe vorgenommen. Das Quenchwasser wird demnach in zwei getrennten Kreisläufen im Umlauf gehalten.Accordingly, the development of a two-stage quench is proposed to solve the problem of the invention of the shock cooling of the high-temperature gas. In two successively located along the flow direction of the high-temperature gas stages or areas of the high-temperature gas flow, the cooling made via two separate cooling circuits. The quench water is therefore kept in circulation in two separate circuits.

Kreislauf 1 dient zur eigentlichen Schockkühlung des Hochtemperaturgases in einem entlang der Strömungsrichtung des Gases ersten Bereich, wobei hier auch die im Gas enthaltenen festen Partikel abgeschieden werden, - Kreislauf 2 dient zur abschließenden Kühlung in einem entlang der Strömungsrichtung des Gases zweiten Bereich auf Endtemperatur.Circuit 1 serves for the actual shock-cooling of the high-temperature gas in a first region along the flow direction of the gas, in which case also the solid particles contained in the gas are separated, - Circuit 2 serves for the final cooling in a second region along the flow direction of the gas to the final temperature.

Erfindungsgemäß ist die Verwendung einer solchen Vorrichtung bzw. eines solchen Verfahrens zur Kühlung von in einem Hochtemperaturrecyclingverfahren anfallenden Synthesegasen vorgesehen.According to the invention, the use of such a device or such a method for cooling obtained in a high-temperature recycling process synthesis gases is provided.

Die vorteilhafte Wirkung der Erfindung besteht in der Lokalisierung der durch die Schockkühlung abgeschiedenen, festen Partikel in einem begrenzten Bereich der Kühlung. Im Zusammenhang mit der im Folgenden genannten Ausführung ist dann sogar die vollkommene Vermeidung von Verschmutzung von Wärmetauschern durch die abgeschiedenen, festen Partikel möglich.The advantageous effect of the invention is the localization of the solid particles precipitated by the shock cooling in a limited range of cooling. In connection with the embodiment mentioned below, even the complete avoidance of contamination of heat exchangers by the separated, solid particles is possible.

Die Quenchwärmetauscher sind ausschließlich im sauberen Kreislauf 2 angeordnet. Über diese Quenchwärmetauscher wird die im Hochtemperaturgas enthaltene Energie abgeführt. Folglich wird der Kreislauf 1, d. i. der eigentliche Quenchkreislauf, ohne Wärmetauscher ausgeführt. Eine Verschmutzung des ersten Kühlkreislaufes ist somit weitgehend ausgeschlossen.The quench heat exchangers are arranged exclusively in the clean circuit 2. About this Quenchwärmetauscher the energy contained in the high-temperature gas is dissipated. Consequently, the circuit 1, d. i. the actual quench circuit, without heat exchanger. Contamination of the first cooling circuit is thus largely excluded.

Es handelt sich bei der Quenchvorrichtung um einen schlanken Apparat mit einem konzentrisch angeordneten Innenrohr, wobei das heiße Gas von oben in das Innenrohr eintritt und den Apparat von oben nach unten durchströmt. Im unteren Bereich wird das Gas durch eine Umlenkungsvorrichtung umgelenkt, durchströmt danach den äußeren Ringspalt nach oben und verlässt den Apparat am oberen Ende. Die Abkühlung im Innenrohr erfolgt vorzugsweise von 1000 °C bis 2000 °C auf 95 °C bis 70 °C, besonders bevorzugt 85 °C, und im äußeren Ringspalt von 85 °C auf 70 bis 40, vorzugsweise 60 °C.The quench device is a slender apparatus with a concentrically arranged inner tube, wherein the hot gas From above into the inner tube enters and flows through the apparatus from top to bottom. In the lower area, the gas is deflected by a deflection device, then flows through the outer annular gap upwards and leaves the apparatus at the upper end. The cooling in the inner tube is preferably carried out from 1000 ° C to 2000 ° C to 95 ° C to 70 ° C, more preferably 85 ° C, and in the outer annular gap of 85 ° C to 70 to 40, preferably 60 ° C.

Gemäß der Erfindung wird über einen freien Überlauf vom Kreislauf 2 in den Kreislauf 1 Quenchwasser abgeführt.According to the invention quench water is discharged via a free overflow from the circuit 2 in the circuit 1.

In einer weiteren bevorzugten Ausführung erfolgt die Niveaukontrolle der beiden, im Kreislauf 1 und Kreislauf 2 bestehenden Quenchwasserstände über den Quenchwasserstand im Kreislauf 1.
Der Mechanismus der Niveauregulierung wird vorzugsweise durch die Zu- oder Abfuhr von Wasser aus dem Kreislauf 1 realisiert.In a further preferred embodiment, the level control of the two quench water levels existing in the circuit 1 and circuit 2 takes place via the quench water level in the circuit 1.
The mechanism of the level control is preferably realized by the supply or removal of water from the circuit 1.

Vorzugsweise werden in dem erfindungsgemäßen Verfahren Rauchgase mit Temperaturen von 1000 °C bis 2000 °C, vorzugsweise 1200 °C schockgekühlt. Die Quenchung führt das Hochtemperaturgas von mehr als 1200 °C auf 95 °C bis 70 °C, vorzugsweise 85 °C im ersten, vorzugsweise aus einem Innenrohr bestehenden Bereich.In the process according to the invention, flue gases having temperatures of 1000 ° C. to 2000 ° C., preferably 1200 ° C., are preferably shock-cooled. The quenching leads the high-temperature gas of more than 1200 ° C to 95 ° C to 70 ° C, preferably 85 ° C in the first, preferably consisting of an inner tube area.

Vorzugsweise wird das Verfahren für Abgase mit einem Wassergehalt von 10 Vol% bis 70 Vol%, besonders bevorzugt 30 Vol%, durchgeführt.The process is preferably carried out for waste gases having a water content of 10% by volume to 70% by volume, particularly preferably 30% by volume.

Claims (11)

  1. Quench device for suddenly cooling streams of hot gas with the aid of quench water, the quench device having a gas supply line and a gas drainage pipe, and the quench water being cooled at least partially by means of a heat exchanger,
    characterised in that
    the quench device is provided with a cooling water circuit cooling a first area of the gas stream and with a separate second cooling water circuit cooling an area of the gas stream downstream from the first area,
    the first area of the gas stream is delimited by the inner wall of a cylindrical inner pipe standing upright, the gas supply line for the quench device lying at the upper end of the pipe, and
    the second area of the gas stream is delimited by the outer wall of the inner pipe and by the inner wall of an outer pipe arranged concentrically around the inner pipe, wherein
    a deflection device is arranged, attached to the lower region of the inner pipe, to deflect a gas stream flowing downwards in the inner pipe in a gas stream flowing upwards in the outer pipe, wherein
    solely the second cooling circuit is provided with heat exchangers cooling the quench water.
  2. Device according to claim 1, characterised in that there is an overflow from the second cooling circuit into the first cooling circuit.
  3. Device according to one of the preceding claims, characterised in that a mechanism is provided for controlling the level of the quench water in the first cooling circuit.
  4. Device according to claim 3, characterised in that the mechanism for controlling the level of the quench water in the first cooling circuit includes regulating the level of the quench water by means of supplying quench water to and discharging quench water from the first circuit.
  5. Method for suddenly cooling a hot gas stream by the addition of quench water according to one of the preceding claims, characterised in that the cooling is effected in a first area of the gas stream by quench water from a first cooling circuit and the cooling is effected in a second area of the gas stream lying downstream of the first area, by quench water from a second cooling water circuit, separate from the first cooling water circuit.
  6. Method according to claim 5, characterised in that solely the quench water in the second cooling circuit is cooled by means of a heat exchanger.
  7. Method according to claim 5 or claim 6, characterised in that the gas in the first area of the gas stream flows in the reverse direction from the gas in the second area of the gas stream.
  8. Method according to one of claims 5 to 7, characterised in that the gases in the first area of the gas stream have an initial temperature before cooling of 1000°C to 2000°C, preferably of 1200°C, and after cooling a temperature of 95°C to 70°C, preferably of 85°C.
  9. Method according to one of claims 5 to 8, characterised in that the gases in the second area of the gas stream have an initial temperature before cooling of 95°C to 70°C, preferably 85°C and after cooling a temperature of 70°C to 40°C, preferably 60°C.
  10. Method according to one of claims 5 to 9, characterised in that the gases to be cooled have a water content of 10 to 70% by volume, preferably 30% by volume.
  11. Use of a device according to one of claims 1 to 4 and a method according to one of claims 5 to 10 for the sudden cooling of synthesis gases occurring in a high-temperature recycling process.
EP04714282A 2003-04-11 2004-02-25 Method for suddenly cooling high-temperature gas Expired - Lifetime EP1613912B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
SI200431190T SI1613912T1 (en) 2003-04-11 2004-02-25 Method for suddenly cooling high-temperature gas

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10316874A DE10316874B4 (en) 2003-04-11 2003-04-11 Process for the shock cooling of high-temperature gases
PCT/EP2004/001879 WO2004090447A1 (en) 2003-04-11 2004-02-25 Method for suddenly cooling high-temperature gas

Publications (2)

Publication Number Publication Date
EP1613912A1 EP1613912A1 (en) 2006-01-11
EP1613912B1 true EP1613912B1 (en) 2009-04-29

Family

ID=33103347

Family Applications (1)

Application Number Title Priority Date Filing Date
EP04714282A Expired - Lifetime EP1613912B1 (en) 2003-04-11 2004-02-25 Method for suddenly cooling high-temperature gas

Country Status (11)

Country Link
EP (1) EP1613912B1 (en)
JP (1) JP2006522911A (en)
KR (1) KR20060004662A (en)
CN (1) CN1768243A (en)
AT (1) ATE430295T1 (en)
DE (2) DE10316874B4 (en)
DK (1) DK1613912T3 (en)
ES (1) ES2323640T3 (en)
PT (1) PT1613912E (en)
SI (1) SI1613912T1 (en)
WO (1) WO2004090447A1 (en)

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2352561C2 (en) * 1973-10-19 1983-02-17 Linde Ag, 6200 Wiesbaden Method for dissipating the compression heat that arises when compressing a gas mixture
DE2416167A1 (en) * 1974-04-03 1976-02-05 Werner Ing Grad Minkler Cooling and partial drying of hot moist gases - by direct cooling with pre-cooled condensate
DE2538611C2 (en) * 1975-08-29 1983-09-08 Linde Ag, 6200 Wiesbaden Process for cooling a raw gas mixture containing different boiling hydrocarbons
GB2065500B (en) * 1979-12-19 1983-09-28 Heat Extractor Corp Heat extractor
US5765546A (en) * 1996-05-30 1998-06-16 Sofame Direct contact water heater with dual water heating chambers
DE19633830C2 (en) * 1996-08-22 2002-01-17 Intensiv Filter Gmbh Cooling device based on the evaporation principle for hot, dusty gases
SE514866C2 (en) * 1997-09-23 2001-05-07 Svensk Roekgasenergi Intressen Device for cooling gases
DE10004138C2 (en) * 2000-01-31 2002-05-16 Thermoselect Ag Vaduz Process and device for the disposal and recycling of waste goods

Also Published As

Publication number Publication date
CN1768243A (en) 2006-05-03
JP2006522911A (en) 2006-10-05
DK1613912T3 (en) 2009-06-22
DE10316874B4 (en) 2008-04-03
ES2323640T3 (en) 2009-07-22
KR20060004662A (en) 2006-01-12
ATE430295T1 (en) 2009-05-15
PT1613912E (en) 2009-06-09
DE502004009424D1 (en) 2009-06-10
DE10316874A1 (en) 2004-11-04
WO2004090447A1 (en) 2004-10-21
SI1613912T1 (en) 2009-10-31
EP1613912A1 (en) 2006-01-11

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