EP0858495A1 - Verfahren zum betreiben einer verbrennungsanlage eines kohlekraftwerkes mit schmelzkammerfeuerung sowie danach arbeitende verbrennungsanlage - Google Patents
Verfahren zum betreiben einer verbrennungsanlage eines kohlekraftwerkes mit schmelzkammerfeuerung sowie danach arbeitende verbrennungsanlageInfo
- Publication number
- EP0858495A1 EP0858495A1 EP96929184A EP96929184A EP0858495A1 EP 0858495 A1 EP0858495 A1 EP 0858495A1 EP 96929184 A EP96929184 A EP 96929184A EP 96929184 A EP96929184 A EP 96929184A EP 0858495 A1 EP0858495 A1 EP 0858495A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- coal
- titanium
- containing material
- melting chamber
- combustion
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L9/00—Treating solid fuels to improve their combustion
- C10L9/10—Treating solid fuels to improve their combustion by using additives
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES
- F23J7/00—Arrangement of devices for supplying chemicals to fire
-
- 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
-
- 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
- C10L10/02—Use of additives to fuels or fires for particular purposes for reducing smoke development
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23B—METHODS OR APPARATUS FOR COMBUSTION USING ONLY SOLID FUEL
- F23B5/00—Combustion apparatus with arrangements for burning uncombusted material from primary combustion
- F23B5/02—Combustion apparatus with arrangements for burning uncombusted material from primary combustion in main combustion chamber
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S44/00—Fuel and related compositions
- Y10S44/905—Method involving added catalyst
Definitions
- the invention relates to a method for operating a combustion plant of a coal-fired power plant with melting chamber firing. It also relates to an incinerator to carry out the process.
- Fly dust can be used as an additive in the construction industry. According to DE 31 28 903 AI, it has already been proposed to use various metal oxides as an additive to improve combustion in dry combustion.
- the combustion temperature in the combustion chamber which in this case is also referred to as the melting chamber, is above the melting temperature of the ash. Under normal operating conditions, this is approx. 1500 ° C.
- the ash melting temperature of the coal used for firing can vary widely and is essentially dependent on the content of aluminum oxide Al2O3 and silicate SiC> 2.
- the majority of the ashes combine to form a melt flow at the bottom of the combustion chamber and are supplied to wet purifiers via outlet openings below. These are water basins in which the leaking liquid ash is caught and quenched.
- the granulate is a renowned material in road construction and is used, for example, as bulk material, but also as a grit or blasting agent.
- the fly ash entrained by the flue gas stream which can consist of up to 50% of combustible material (carbon and / or semi-burned hydrocarbons), is separated in the electrostatic filters.
- the temperature of the combustion or melting chamber and the melting temperature of the ash must be coordinated for particularly effective melting chamber operation, ie complete burnout, rapid fuel conversion and avoidance of NO x formation.
- the composition of the coal (depending on the composition, the ash melting temperature varies between 1300 ° C and 1700 ° C) determines the design of the coal-fired power plant, such as the size of the combustion chamber. By adding limestone, however, it is possible to lower the melting temperatures of the ash. Experience shows that by adding approx. 2% limestone to coal, the melting temperature of the ash can be reduced by approx. 100 ° C. This procedure provides a regulation for the operation of the furnace.
- the fly ash is blown into the combustion chamber again via a separate fly ash recirculation in modern coal-fired power plants which operate according to the melting chamber method.
- the entire ashes of the combustion or melting chamber accumulate as slag and can be disposed of in the usual way.
- a complete burnout of the fuel is achieved by the fly ash recirculation, but the average residence time of a coal or ash particle in the combustion circuit increases.
- the disadvantage is the maximum Throughput of coal and thus the possible output of the power plant is limited.
- the invention is therefore based on the object of creating an inexpensive method for operating a coal-fired power plant, which works according to the method of melting furnace firing, with which the throughput of fuel and thus the performance of the power plant can be increased. This is to be achieved with an incineration plant suitable for carrying out the method using particularly simple means.
- this object is achieved according to the invention in that a titanium-containing material is supplied to the coal in addition to the coal in order to accelerate the coal burnout.
- titanium measured as titanium dioxide TiO 2
- the invention is based on the observation that titanium dioxide can increase the burnout of the coal in the combustion chamber and thus the throughput of coal, which in turn leads to an increase in the performance of the power plant.
- the viscosity and the melting temperature of the ash should not be changed significantly by the addition of titanium-containing materials.
- titanium which is present as titanium dioxide under the conditions of the melting chamber, should not favor slag-like approaches behind the combustion chamber which adhere to pipes and walls. It has been shown that titanium dioxide lowers the melting point of the ash or slag. A sand-like, unmelted and non-sticking dust could thereby become a tough, flowing and sticky melt, which leads to higher cleaning costs and financial losses during the maintenance of the coal-fired power station.
- the titanium dioxide is largely reflected in the liquid ash. finds.
- titanium contents (measured as titanium dioxide) of less than about 3% in the total amount of coal and titanium-containing material supplied, the consistency of the slag-like preparations does not change, since the titanium dioxide is now practically only in the liquid ash.
- the titanium dioxide content in the total amount of coal and titanium-containing materials added is at most 2.25%.
- the supplied titanium-containing material advantageously consists of more than 50% titanium dioxide.
- a titanium dioxide: carbon ratio of at least 1:99 is advantageous.
- the titanium added is to a small extent excreted via fly ash, but predominantly via liquid ash. Since titanium dioxide is not toxic, not only the liquid ash, but also the fly ash can continue to be used as usual. If the coal-fired power plant works with a fly ash return, the fly ash formed is returned to the furnace, so that the titanium is practically exclusively excreted as titanium dioxide together with the liquid ash formed.
- the titanium-containing material is advantageously added to the coal, after which it can be ground in a coal mill of the power plant and introduced into the combustion chamber of the power plant via a coal belt via the burners. However, the titanium-containing material can also be blown into the combustion chamber pneumatically, preferably via the fly ash return, in a particularly simple manner.
- DeNO x catalysts used as titanium-containing material, ie DeNO x catalysts or waste products to be disposed of, e.g. B. the titanium processing industry used.
- DeNO x catalysts there is a cheaper, environmentally friendly disposal route, since otherwise costs are incurred through landfilling or expensive reprocessing measures.
- heavy metals in particular arsenic
- Such leaching was not found in a DeNO ⁇ catalyst with 4.5% molybdenum, so that restrictions can only arise for catalysts with such a high molybdenum content.
- the above-mentioned object is achieved by accelerating the
- Coal burnout can be supplied via a separate feed line in addition to coal containing titanium-containing material.
- FIG. 1 shows a schematic representation of a combustion plant of a coal-fired power plant with a melting chamber, a coal mill, a DeNO x plant and a granulate production
- FIG. 2 shows a coal-fired power plant according to FIG. 1 with a fly ash return
- FIG. 1 of a first exemplary embodiment of the invention is part of a coal-fired power plant (not shown in more detail).
- It comprises a high-temperature combustion chamber designed as a melting chamber 2 with at least one burner 2a, and with a feed 2b, for example a conveyor belt for the coal K, and a fresh air line 4 guided over a compressor 3 A discharge line 5 for liquid ash F with a wet descaler 6 connected to it. It also comprises a flue gas line 7 and, in series with the flue gas line 7, a dust filter system 8 with a fly ash collector 9, a flue gas desulfurization system 10 and a catalytic denoxification system 11 The flue gas line 7 opens into a chimney 12.
- the feed 2b is connected to a coal mill 13 which is connected to a feed shaft 14 of a coal store 15 and to a separate feed line 16 for adding titanium-containing material M.
- the burn-out acceleration of the coal K in the combustion chamber 2 is adjusted via the amount of titanium-containing material M.
- the coal K is conveyed from the coal store 15 via the feed shaft 14 into the coal mill 13.
- the titanium-containing material M is either introduced via the feed line 16 and the feed shaft 14 or directly into the coal mill 13 and there, together with the coal K, is ground very finely.
- Fuel B prepared in this way reaches the combustion chamber 2 via the feed 2b and the burner 2a, where it is burned with compressed air L supplied via the fresh air line 4.
- the resulting flue gas RG flows via the flue gas line 7 into the dust filter system 8, where fly ash or fly dust S entrained by the flue gas is intercepted and discharged via the fly ash collector 9.
- the liquid ash F collecting on the combustion chamber floor 2c is fed to the wet slipper 6 via the discharge line 5 and processed into granules G.
- the fly ash S collected at the collector 9 can be used as usual. Up to 3% titanium-containing material M with a titanium dioxide content of more than 50% is advantageously used. Aggregates or impurities contained in this material M, e.g. Heavy metals are melted insoluble in the granules G obtained. These melt chamber granules G can be used as building material as usual.
- the combustion system 1 also has
- Melting chamber firing a fly ash return 20 on This opens directly into the combustion chamber 2 of the melting chamber furnace.
- the fly ash S retained in the dust filter system 8 via the collector 9 is blown pneumatically into the combustion chamber 2 with the aid of an additional compressor 21.
- titanium-containing, dust-finely ground material M is added to the fly ash S and passes into the combustion chamber 2 with it.
- Fly ash return 20 is particularly effective burnout while simultaneously accelerating the throughput of coal K in the power plant. This increases the performance of the power plant.
- Example 1 Used DeNO x catalysts are used as the titanium-containing material M and mixed with coal K.
- a highly decarburized, high-ballast hard coal is used as coal K, which, according to its degree of decarburization and the proportion of volatile components, belongs to lean coal and lies on the border between lean coal and anthracite coal. The ashes of this coal show normal melting behavior.
- the catalyst used consists of approximately 75% TiC> 2 and contains additional catalytic components (approximately 11% SiO2, approximately 8% WO3 and approximately 1.8% V2O5).
- combustion tests are carried out in a combustion chamber 2.
- the combustion chamber 2 is designed as a laboratory combustion chamber, each with a liquid ash extractor and a dry ash extractor.
- the composition of the ash, the influencing of the slagging behavior of the coal by adding used catalyst, the influence of the catalyst fraction M on the slagging intensity of the heating surfaces behind the combustion chamber and the distribution of the catalyst material in the combustion residues are examined. An X-ray fluorescence analysis of these combustion residues is carried out.
- FIGS. 3 to 7 show the test results for the combustion chamber with liquid ash extraction.
- Curves c, d and e of FIGS. 5 to 7 show the percentage of active catalyst substances TiC> 2 (FIG. 5), V2O5 (FIG. 6) and WO3 (FIG. 7) in the slag F, in the fly ash S and in the slag-like approaches.
- Another surprising result is that the catalyst is found primarily in the slag or liquid ash F (curve c, FIGS. 5 to 7) and partly in the fly ash S (curve d, FIGS. 5 to 7), but hardly in the slag-like form Approaches (curve e, Figures 5 to 7) takes place.
- catalyst M ⁇ (0 to 3%) in the fuel, only the proportions of TiC> 2 (FIG. 5), V2O5 (FIG. 6) and WO3 increase
- Example 2 Fly ash from an electrostatic precipitator of a coal-fired power plant with melting chamber firing is mixed with calcium carbonate (CaCC> 3) in a mass ratio of 100: 5. As a result, a melt can be obtained directly ("zero test”). The same mixture is mixed for comparison with used, finely ground DeNO x catalyst in such a way that the catalyst fraction is 1%. The mixture is melted at 1550 ° C for 20 minutes and quenched in water ("comparative sample”). 5 g of the granules G obtained are eluted with 50 g of H2O for 24 hours and the eluate is examined for traces of vanadium V, tungsten W and arsenic A ⁇ .
- the amount of active catalyst substances (V, W) washed out from the comparison sample is below the detection limit ( ⁇ 0.1 mg / l).
- the arsenic content is in the same range for both samples.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- General Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Gasification And Melting Of Waste (AREA)
- Processing Of Solid Wastes (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
- Solid Fuels And Fuel-Associated Substances (AREA)
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19534558A DE19534558C1 (de) | 1995-09-18 | 1995-09-18 | Additiv zum Verbrennen von Kohle in einem Kohlekraftwerk mit Schmelzkammerfeuerung |
DE19534558 | 1995-09-18 | ||
PCT/DE1996/001721 WO1997011139A1 (de) | 1995-09-18 | 1996-09-12 | Verfahren zum betreiben einer verbrennungsanlage eines kohlekraftwerkes mit schmelzkammerfeuerung sowie danach arbeitende verbrennungsanlage |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0858495A1 true EP0858495A1 (de) | 1998-08-19 |
EP0858495B1 EP0858495B1 (de) | 2003-07-02 |
Family
ID=7772466
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP96929184A Expired - Lifetime EP0858495B1 (de) | 1995-09-18 | 1996-09-12 | Verwendung eines verfahrens zum betreiben einer verbrennungsanlage eines kohlekraftwerkes zur beschleunigung des kohleausbrendes einer schmelzkammer |
Country Status (12)
Country | Link |
---|---|
US (1) | US6067914A (de) |
EP (1) | EP0858495B1 (de) |
JP (1) | JP2989272B2 (de) |
KR (1) | KR19990045747A (de) |
CN (1) | CN1197477A (de) |
AT (1) | ATE244292T1 (de) |
CA (1) | CA2232476A1 (de) |
DE (2) | DE19534558C1 (de) |
ES (1) | ES2202461T3 (de) |
RU (1) | RU2152428C1 (de) |
TW (1) | TW301698B (de) |
WO (1) | WO1997011139A1 (de) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4909296B2 (ja) * | 2008-02-12 | 2012-04-04 | 三菱重工業株式会社 | 重質燃料焚ボイラシステム及びその運転方法 |
CN101524695B (zh) * | 2009-04-03 | 2011-06-08 | 沈阳航空工业学院 | 利用电厂飞灰生产漂珠的方法 |
WO2015060795A1 (en) * | 2013-10-21 | 2015-04-30 | Dora Teknolojik Bilgisayar Ürünleri Endüstrisi Anonim Şirketi | Process for the minimization/elimination of so2 and co2 emission emerging from the combustion of coal |
CN106635242A (zh) * | 2016-12-07 | 2017-05-10 | 江西稀有金属钨业控股集团有限公司 | 一种白钨精矿冶炼渣的利用方法、利用装置及用途 |
CN114574262B (zh) * | 2022-03-04 | 2022-12-13 | 安徽工业大学 | 一种利用钛白废酸生产的燃煤催化剂及其制备方法 |
Family Cites Families (25)
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US1947460A (en) * | 1927-01-31 | 1934-02-20 | Coutant Jay Gould | Pulverized fuel furnace and method of combustion |
CH253222A (de) * | 1945-11-08 | 1948-02-29 | Rothenbach Walter Ing Dipl | Verfahren zur Herstellung eines Brennstoffes. |
BE703706A (de) * | 1967-09-11 | 1968-02-01 | ||
GB1402207A (en) * | 1972-03-03 | 1975-08-06 | Siemens Ag | Catalyst and its use in hydrocarbon cracking processes |
US4057398A (en) * | 1976-02-24 | 1977-11-08 | Apollo Chemical Corporation | Process for reducing the fusion point of coal ash |
US4388877A (en) * | 1981-07-07 | 1983-06-21 | Benmol Corporation | Method and composition for combustion of fossil fuels in fluidized bed |
DE3128903C2 (de) * | 1981-07-22 | 1983-09-08 | L. & C. Steinmüller GmbH, 5270 Gummersbach | "Verfahren zum Eintragen von Additiv in einen Reaktionsgasstrom" |
US4377118A (en) * | 1981-12-21 | 1983-03-22 | Nalco Chemical Company | Process for reducing slag build-up |
US4577566A (en) * | 1982-04-01 | 1986-03-25 | Betz Laboratories, Inc. | Method of conditioning fireside fouling deposits using large particle size amorphous silica |
DE3504122C2 (de) * | 1985-02-07 | 1994-02-03 | Kat Tec Ges Fuer Katalysatorte | Katalysator zur Umwandlung von Kohlenwasserstoffen, Stickoxiden und Brenngasen |
JPS6348392A (ja) * | 1986-08-15 | 1988-03-01 | Toa Netsuken Kk | 石炭の排ガスダストのクリンカ−アツシユ抑制方法 |
DE3635027A1 (de) * | 1986-10-15 | 1988-04-28 | Steinmueller Gmbh L & C | Direktentschwefelungsverfahren mit flugstaubrueckfuehrung |
US4771712A (en) * | 1987-06-24 | 1988-09-20 | A. Ahlstrom Corporation | Combustion of fuel containing alkalines |
DE3741604C1 (de) * | 1987-12-09 | 1989-02-23 | Metallgesellschaft Ag | Verfahren zur Abscheidung der Asche aus dem bei der Verbrennung von Kohle anfallenden Gas |
ES2054882T3 (es) * | 1988-01-14 | 1994-08-16 | Siemens Ag | Procedimiento y dispositivo para la purificacion de gases de humo. |
US4836117A (en) * | 1988-01-15 | 1989-06-06 | The Standard Oil Company | Oxidation catalyst and processes using same |
US4843980A (en) * | 1988-04-26 | 1989-07-04 | Lucille Markham | Composition for use in reducing air contaminants from combustion effluents |
US4979447A (en) * | 1988-06-08 | 1990-12-25 | Velino Ventures Inc. | Combustion of carbon containing materials in a furnace |
JPH03244692A (ja) * | 1990-02-23 | 1991-10-31 | Taiho Ind Co Ltd | 燃料添加剤 |
DE4013720C2 (de) * | 1990-04-28 | 1994-05-19 | Huels Chemische Werke Ag | Verfahren zur Verwertung von gebrauchten DeNOx-Katalysatoren |
DE4021362A1 (de) * | 1990-07-05 | 1992-01-09 | Siemens Ag | Verfahren und vorrichtung zur entsorgung von mit schadstoffen beladenen rueckstaenden |
DE4209166A1 (de) * | 1992-03-20 | 1993-09-23 | Siemens Ag | Verfahren und einrichtung zur katalytischen entfernung von schadstoffen aus rauchgas |
US5309850A (en) * | 1992-11-18 | 1994-05-10 | The Babcock & Wilcox Company | Incineration of hazardous wastes using closed cycle combustion ash vitrification |
DE4301814A1 (de) * | 1993-01-23 | 1994-07-28 | Steinmueller Gmbh L & C | Verfahren zum Verbrennen eines im wesentlichen aus Kunststoff bestehenden Abfalls, insbesondere PVC-Abfall |
US5819672A (en) * | 1995-04-06 | 1998-10-13 | Addchem Systems | Treatment to enhance heat retention in coal and biomass burning furnaces |
-
1995
- 1995-09-18 DE DE19534558A patent/DE19534558C1/de not_active Expired - Fee Related
-
1996
- 1996-09-12 AT AT96929184T patent/ATE244292T1/de not_active IP Right Cessation
- 1996-09-12 EP EP96929184A patent/EP0858495B1/de not_active Expired - Lifetime
- 1996-09-12 WO PCT/DE1996/001721 patent/WO1997011139A1/de not_active Application Discontinuation
- 1996-09-12 CN CN96197176A patent/CN1197477A/zh active Pending
- 1996-09-12 ES ES96929184T patent/ES2202461T3/es not_active Expired - Lifetime
- 1996-09-12 CA CA002232476A patent/CA2232476A1/en not_active Abandoned
- 1996-09-12 JP JP9512311A patent/JP2989272B2/ja not_active Expired - Fee Related
- 1996-09-12 DE DE59610578T patent/DE59610578D1/de not_active Expired - Lifetime
- 1996-09-12 RU RU98107258/12A patent/RU2152428C1/ru not_active IP Right Cessation
- 1996-09-12 KR KR1019980701990A patent/KR19990045747A/ko not_active Application Discontinuation
- 1996-09-18 TW TW085111387A patent/TW301698B/zh active
-
1998
- 1998-03-18 US US09/040,970 patent/US6067914A/en not_active Expired - Lifetime
Non-Patent Citations (1)
Title |
---|
See references of WO9711139A1 * |
Also Published As
Publication number | Publication date |
---|---|
WO1997011139A1 (de) | 1997-03-27 |
DE19534558C1 (de) | 1996-11-07 |
CA2232476A1 (en) | 1997-03-27 |
ATE244292T1 (de) | 2003-07-15 |
RU2152428C1 (ru) | 2000-07-10 |
US6067914A (en) | 2000-05-30 |
ES2202461T3 (es) | 2004-04-01 |
TW301698B (de) | 1997-04-01 |
JPH11502897A (ja) | 1999-03-09 |
KR19990045747A (ko) | 1999-06-25 |
JP2989272B2 (ja) | 1999-12-13 |
DE59610578D1 (de) | 2003-08-07 |
CN1197477A (zh) | 1998-10-28 |
EP0858495B1 (de) | 2003-07-02 |
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