EP1664353B1 - Procede et installation pour granuler des scories - Google Patents

Procede et installation pour granuler des scories Download PDF

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Publication number
EP1664353B1
EP1664353B1 EP04765337A EP04765337A EP1664353B1 EP 1664353 B1 EP1664353 B1 EP 1664353B1 EP 04765337 A EP04765337 A EP 04765337A EP 04765337 A EP04765337 A EP 04765337A EP 1664353 B1 EP1664353 B1 EP 1664353B1
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EP
European Patent Office
Prior art keywords
water
slag
granulation
condensation
gases
Prior art date
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Expired - Lifetime
Application number
EP04765337A
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German (de)
English (en)
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EP1664353B2 (fr
EP1664353A1 (fr
Inventor
Bogdan Vuletic
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.)
SIEMENS VAI METALS Technologies GmbH
Original Assignee
Voest Alpine Industrienlagenbau GmbH
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Publication date
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Application filed by Voest Alpine Industrienlagenbau GmbH filed Critical Voest Alpine Industrienlagenbau GmbH
Priority to PL04765337T priority Critical patent/PL1664353T5/pl
Publication of EP1664353A1 publication Critical patent/EP1664353A1/fr
Application granted granted Critical
Publication of EP1664353B1 publication Critical patent/EP1664353B1/fr
Publication of EP1664353B2 publication Critical patent/EP1664353B2/fr
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Classifications

    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21BMANUFACTURE OF IRON OR STEEL
    • C21B3/00General features in the manufacture of pig-iron
    • C21B3/04Recovery of by-products, e.g. slag
    • C21B3/06Treatment of liquid slag
    • C21B3/08Cooling slag
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21BMANUFACTURE OF IRON OR STEEL
    • C21B2100/00Handling of exhaust gases produced during the manufacture of iron or steel
    • C21B2100/40Gas purification of exhaust gases to be recirculated or used in other metallurgical processes
    • C21B2100/42Sulphur removal
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21BMANUFACTURE OF IRON OR STEEL
    • C21B2400/00Treatment of slags originating from iron or steel processes
    • C21B2400/02Physical or chemical treatment of slags
    • C21B2400/022Methods of cooling or quenching molten slag
    • C21B2400/024Methods of cooling or quenching molten slag with the direct use of steam or liquid coolants, e.g. water
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21BMANUFACTURE OF IRON OR STEEL
    • C21B2400/00Treatment of slags originating from iron or steel processes
    • C21B2400/02Physical or chemical treatment of slags
    • C21B2400/03Removing sulfur
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21BMANUFACTURE OF IRON OR STEEL
    • C21B2400/00Treatment of slags originating from iron or steel processes
    • C21B2400/02Physical or chemical treatment of slags
    • C21B2400/032Separating slag from liquid, e.g. from water, after quenching
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21BMANUFACTURE OF IRON OR STEEL
    • C21B2400/00Treatment of slags originating from iron or steel processes
    • C21B2400/05Apparatus features
    • C21B2400/062Jet nozzles or pressurised fluids for cooling, fragmenting or atomising slag
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21BMANUFACTURE OF IRON OR STEEL
    • C21B2400/00Treatment of slags originating from iron or steel processes
    • C21B2400/05Apparatus features
    • C21B2400/066Receptacle features where the slag is treated
    • C21B2400/072Tanks to collect the slag, e.g. water tank
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21BMANUFACTURE OF IRON OR STEEL
    • C21B2400/00Treatment of slags originating from iron or steel processes
    • C21B2400/05Apparatus features
    • C21B2400/066Receptacle features where the slag is treated
    • C21B2400/074Tower structures for cooling, being confined but not sealed

Definitions

  • the invention relates to a method for granulating slag, in particular from a blast furnace and / or a smelting reduction plant, wherein a granulate-water mixture formed during granulation is fed to a granulation vessel and then to a dewatering plant, in which the slag granules are dewatered, and wherein the Granulating resulting H 2 S containing vapors and gases are at least partially condensed in a congruent with the granulating vessel in connection condensing space by injecting water.
  • the hot slag originating from a blast furnace or smelting plant is converted into granules, such as e.g. by rapid cooling and crushing with water.
  • the granulate-water mixture flows through a granulation tank or via a channel to a dewatering plant.
  • the slag sand is dewatered to about 12% and then sold as a finished product.
  • the gas streams consisting of a steam-exhaust steam mixture, which are understood as exhaust air and pollutants such as H 2 S and SO 2 , conducted in a closed circuit and precipitated with calcium oxide-containing water in a condensing tower.
  • the introduced into the system air leads in other areas of the system according to DE 35 11 958 C to a slight overpressure and passes through Granulatabsch- and other openings as well as on hoods in the atmosphere. With the air, however, the harmful gases in concentrations that are above the permitted limits escape uncontrolled into the atmosphere.
  • the sulfur-containing waste gases are subjected to chemical gas scrubbing in a separate apparatus in the condenser tower by means of the injection of an alkaline aqueous solution before they are passed into the atmosphere.
  • chemical gas scrubbing in a separate apparatus in the condenser tower by means of the injection of an alkaline aqueous solution before they are passed into the atmosphere.
  • an additional chemical system and a resulting consumption of chemicals are necessary.
  • the invention aims to avoid the above-mentioned problems and disadvantages and has as its object to provide a method and a plant for granulating slag, in which the H 2 S content of the resulting during the granulation gases and vapors without complicated installations in an existing Reliable system eliminated without additional chemical consumption or at least reduced below the permissible limit concentration. Furthermore, the escape of H 2 S-containing gases from other openings and leaks in the system should be avoided and the amount of air introduced into the system should be minimized.
  • This object is achieved in a method for granulating slag according to the aforementioned type according to the invention in that H 2 S containing residual gases are derived below the water injection from the Kondensierraum and H 2 S is burned.
  • the combustion of H 2 S to SO 2 is carried out in a combustion chamber.
  • a combustion chamber Such can also be easily added to an existing system.
  • the combustion exhaust gas is cooled with water and precipitated from the resulting H 2 S SO 2 .
  • a further preferred variant is characterized in that the residual gases are led after discharge from the Kondensierraum in countercurrent to the hot slag and this H 2 S is burned to SO 2 , optionally with heat supply by means of a support flame.
  • the granulating container is sealed gas-tight with respect to the drainage system.
  • escape of the sulfur-containing gases and vapors formed substantially during the granulation process is prevented in the dewatering system, so that a large part of these gases and vapors is deposited by the injected water in the condenser.
  • an overpressure is set in the granulating container and in the condenser space below the water injection. This is done by setting the water injection.
  • the overpressure has the positive effect that the H 2 S-containing residual gases without forced delivery devices, such as fans and the like., To the downstream combustion point, ie combustion chamber or slag channel, are passed. In addition, the amount of air introduced through the granulator is reduced, and thus also the amount of air and H 2 S cargo discharged from the system.
  • vapors and gases produced in the dewatering plant are passed into the condensation space above the water injection.
  • These vapors and gases, some of which also contain sulfur, can be precipitated in the condenser space or fed to combustion as H 2 S-containing residual gases.
  • a negative pressure is set in the condensing tower above the water injection.
  • a gas barrier is formed, for example, in the granulation tank downstream equipment through a gas line with the Kondensierraum on the Wassereindüsung from a negative pressure, which causes no vapors and gases uncontrollably escape from openings and leaks, but these vapors and gases in the Be condensed condensing.
  • the guided by a suction effect in the Kondensierraum steam and gas quantity is preferably controlled by the amount of injected water and kept to a minimum. This minimizes the amount of H 2 S discharged with the air as well as the energy consumption of the system.
  • a further preferred variant of the invention is characterized in that condensate formed in the condensing space and injected water are removed from the condensing space and supplied to the water separated in the dewatering plant, which is recycled for granulation and water injection.
  • the amount of injected water is appropriately regulated depending on the slag rate.
  • the slag granulating plant comprises a slag chute for conveying the hot slag to a granulating apparatus, preferably a spray head, a granulating vessel arranged thereafter for receiving a granulated water mixture, a condensing means communicating with the granulating tank, preferably one Condensation tower, with a water supply and a device for water injection, and a granular dewatering plant, and is characterized in that in the condenser below the device for water injection a discharge for vapors and gases is provided, which communicates with a combustion chamber in line.
  • the slag granulating plant comprises a slag chute provided with a suction hood for conveying the hot slag to a granulating apparatus, preferably a spray head, a granulating container arranged thereafter for receiving a granulated water mixture, one with the granulating container fluidically connected condensing device, preferably a condensing tower, with a water supply and a device for water injection, and a granular dewatering plant, and is characterized in that in the condenser below the device for water injection a discharge for vapors and gases is provided between the the granulator and the suction hood opens into the slag trough.
  • a water cooler for the combustion exhaust gases is provided after the combustion chamber or after the suction hood of the slag trough.
  • the slag trough comprises a burner for generating a support flame, which can be switched on depending on the slag trough temperature.
  • the slag trough can be heated after a longer standstill to the required for the combustion of H 2 S temperature.
  • a preferred variant of the system according to the invention is characterized in that the granulate dewatering plant comprises at least one dewatering device and a water basin, which are provided with a cover, and leads away from the cover a derivative of vapors and gases, which in the condenser above the device for Water injection opens.
  • a gas barrier is provided between the granulation and the granular dewatering system.
  • a means for collecting water and condensate is provided in the condenser below the device for water injection, from which leads away a derivative, which opens into the granular dewatering device, in particular the water basin.
  • the granulate dewatering plant in particular the water basin, is preferably in line with the water supply of the condensing device and / or the granulator in combination.
  • hot slag from a blast furnace and / or a smelting reduction plant is conveyed through a slag channel 1 in the direction of the arrow to a granulating device 2, for example a spray head, where it is cooled and crushed by the injection of water.
  • the resulting granulate-water mixture passes through a granulating 3 into a granulating 4 and from there through a channel 5 in a granular dewatering system consisting of dewatering devices 6a and 6b, eg screw conveyors, drum filters, etc., and water basin 7a-7c.
  • the granules are dewatered and the slag sand in storage areas 8a and 8b stored.
  • the water deposited in the water tanks 7a-7c is returned to the granulating device 2 via a line 9 after replacement of the losses and cooling in a cooling tower 24 as process water from the collecting tank 23 of the cooling tower 24.
  • the sulfur-containing vapors and gases produced during granulation are precipitated in a condensing tower 10 arranged above the granulation container 4.
  • a device 11 for water injection is arranged, which is supplied via a fed from the collecting tank 23 water supply 12 with calcium oxide-containing water.
  • means 13 for collecting water and condensate e.g. formed by water gutters, arranged, which is connected via a discharge line 14 with the water tank 7c.
  • the non-condensed or precipitated, H 2 S-containing residual gases and vapors are withdrawn below the device 11 and above the means 13 via a discharge line 15 from the condensing tower 10 and fed to a temperature-controlled combustion chamber 16, where a combustion of H 2 S to SO 2 takes place.
  • the combustion exhaust gases are subsequently cooled in a water cooler (or scrubber) 17 fed by the water feed 12 and the SO 2 contained therein is washed out or precipitated.
  • the purified from H 2 S and SO 2 exhaust gas is then passed into the atmosphere.
  • the wash water is fed to the discharge line 14.
  • the discharge line 15 opens in the slag channel 1, specifically between the granulating device 2 and a suction hood 18 provided above the slag channel 1.
  • the residual gases are conducted in the slag channel 1 in countercurrent to the hot slag and H 2 S is SO 2 burned.
  • the distance between the junction of the discharge line 15 in the slag channel 1 and the suction hood 18 ensures that the residual gases can be heated to the required temperature for the combustion of H 2 S and that enough time is available for combustion.
  • a burner 19 is provided in the slag channel 1 for generating a support flame.
  • the combustion exhaust gases are discharged via the suction hood 18 and optionally supplied to the water cooler 17 or a dedusting device.
  • the granulating 4 is compared to the channel 5 and subsequently completed with respect to the granular dewatering system with a gas barrier 20, which allows only the granulate-water mixture a transfer into the channel 5 and the dewatering system, but the vapors and gases in the granulation and retains in the condensing tower 10.
  • the drainage devices 6a, 6b with the water reservoirs 7a and 7b and the last water reservoir 7c are provided with cover hoods 21a-21c, from which a discharge line 21 for possibly resulting sulfur-containing vapors and gases in the dewatering system, which leads above the device 11 into the condensing tower 10 opens.
  • a discharge line 21 for possibly resulting sulfur-containing vapors and gases in the dewatering system which leads above the device 11 into the condensing tower 10 opens.
  • measuring or control devices are provided so that the extracted from the dewatering system steam and gas quantity can be controlled via the amount of water injected into the condenser 10 and kept to a minimum .
  • measuring instruments for determining the slag rate are provided in order to be able to regulate the injected water quantity and also the dependence of these.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Furnace Details (AREA)
  • Manufacture Of Iron (AREA)
  • Processing Of Solid Wastes (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Waste-Gas Treatment And Other Accessory Devices For Furnaces (AREA)

Claims (19)

  1. Procédé pour granuler des scories, en particulier d'un haut fourneau et/ou d'une installation de réduction en fusion, dans lequel un mélange eau-granulat formé lors de la granulation est envoyé à un récipient de granulation (4) et ensuite à une installation d'assèchement, dans laquelle les scories granulées sont asséchées, et dans lequel les vapeurs et les gaz contenant du H2S produits pendant la granulation sont condensés au moins en partie par injection d'eau dans une chambre de condensation communiquant par écoulement avec le récipient de granulation (4), caractérisé en ce que les gaz résiduels contenant du H2S sont déviés hors de la chambre de condensation en dessous de l'injection d'eau et le H2S est brûlé.
  2. Procédé selon la revendication 1, caractérisé en ce que la combustion est effectuée dans une chambre de combustion (16).
  3. Procédé selon la revendication 1, caractérisé en ce qu'après la déviation hors de la chambre de condensation, les gaz résiduels sont conduits à contre-courant par rapport aux scories chaudes et le H2S est ainsi brûlé en SO2, le cas échéant avec apport de chaleur au moyen d'une flamme d'appoint.
  4. Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce que les gaz d'échappement de la combustion sont refroidis à l'eau et le SO2 provenant du H2S est précipité.
  5. Procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce que le récipient de granulation (4) est séparé de façon étanche au gaz par rapport à l'installation d'assèchement.
  6. Procédé selon l'une quelconque des revendications 1 à 5, caractérisé en ce que l'on établit une surpression dans le récipient de granulation (4) et dans la chambre de condensation en dessous de l'injection d'eau.
  7. Procédé selon l'une quelconque des revendications 1 à 6, caractérisé en ce que les vapeurs et les gaz produits dans l'installation d'assèchement sont conduits dans la chambre de condensation au-dessus de l'injection d'eau.
  8. Procédé selon la revendication 7, caractérisé en ce que l'on établit une dépression dans la chambre de condensation au-dessus de l'injection d'eau.
  9. Procédé selon la revendication 7 ou 8, caractérisé en ce que la quantité de vapeurs et de gaz conduite dans la chambre de condensation au moyen d'un effet d'aspiration est régulée par la quantité d'eau injectée et est maintenue à un niveau minimum.
  10. Procédé selon l'une quelconque des revendications 1 à 9, caractérisé en ce que le condensat formé dans la chambre de condensation et l'eau injectée sont évacués hors de la chambre de condensation et ajoutés à l'eau précipitée dans l'installation d'assèchement, qui est recyclée pour la granulation et pour l'injection d'eau.
  11. Procédé selon l'une quelconque des revendications 1 à 10, caractérisé en ce que la quantité d'eau injectée est régulée en fonction du débit de scories.
  12. Installation pour granuler des scories, en particulier d'un haut fourneau et/ou d'une installation de réduction en fusion, comprenant un canal à scories (1) pour transporter les scories chaudes vers un dispositif (2) de granulation, de préférence une tête de projection, un récipient de granulation (4) disposé ensuite pour recueillir un mélange eau-granulat, un dispositif de condensation (10) communiquant en écoulement avec le récipient de granulation (4), de préférence une tour de condensation, avec une arrivée d'eau (12) et un dispositif (11) pour l'injection d'eau, et une installation d'assèchement du granulat, caractérisée en ce qu'il est prévu dans le dispositif de condensation (10), en dessous du dispositif (11) pour l'injection d'eau, une conduite d'évacuation (15) pour les vapeurs et les gaz, qui est en liaison de communication avec une chambre de combustion (16).
  13. Installation pour granuler des scories, en particulier d'un haut fourneau et/ou d'une installation de réduction en fusion, comprenant un canal à scories (1) pourvu d'une hotte aspirante (18) pour transporter les scories chaudes vers un dispositif (2) de granulation, de préférence une tête de projection, un récipient de granulation (4) disposé ensuite pour recueillir un mélange eau-granulat, un dispositif de condensation (10) communiquant en écoulement avec le récipient de granulation (4), de préférence une tour de condensation, avec une arrivée d'eau (12) et un dispositif (11) pour l'injection d'eau, et une installation d'assèchement du granulat, caractérisée en ce qu'il est prévu dans le dispositif de condensation (10), en dessous du dispositif (11) pour l'injection d'eau, une conduite d'évacuation (15) pour les vapeurs et les gaz, qui débouche dans le canal à scories (1) entre le dispositif de granulation (2) et la hotte aspirante (18).
  14. Installation selon la revendication 12 ou 13, caractérisée en ce qu'il est prévu, après la chambre de combustion (16) ou après la hotte aspirante (18) du canal à scories (1) un refroidisseur à l'eau (17) pour les gaz d'échappement de la combustion.
  15. Installation selon la revendication 13 ou 14, caractérisé en ce que le canal à scories (1) comporte un brûleur (19) pour la production d'une flamme d'appoint.
  16. Installation selon l'une quelconque des revendications 12 à 15, caractérisé en ce que l'installation d'assèchement de granulat comprend au moins un dispositif d'assèchement (6a, 6b) et un bassin à eau (7a, 7b, 7c), qui sont pourvus d'une hotte de recouvrement (21a, 21b, 21c), et de la hotte de recouvrement (21a, 21b, 21c) part une conduite d'évacuation (22) pour des vapeurs et des gaz, qui débouche dans le dispositif de condensation (10) au-dessus du dispositif (11) pour l'injection d'eau.
  17. Installation selon l'une quelconque des revendications 12 à 16, caractérisée en ce qu'il est prévu un barrage à gaz (20) entre le récipient de granulation (4) et l'installation d'assèchement du granulat.
  18. Installation selon l'une quelconque des revendications 12 à 17, caractérisée en ce qu'il est prévu dans le dispositif de condensation (10), en dessous du dispositif (11) pour l'injection d'eau, un moyen (13) pour capter l'eau et le condensat, duquel part une conduite d'évacuation (14) qui débouche dans le dispositif d'assèchement du granulat, en particulier dans le bassin à eau (7c).
  19. Installation selon l'une quelconque des revendications 12 à 18, caractérisée en ce que l'installation d'assèchement du granulat, en particulier le bassin à eau (7c), est en liaison de communication avec l'arrivée d'eau (12) du dispositif de condensation (10) et/ou du dispositif de granulation (2).
EP04765337A 2003-09-25 2004-09-17 Procede et installation pour granuler des scories Expired - Lifetime EP1664353B2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL04765337T PL1664353T5 (pl) 2003-09-25 2004-09-17 Sposób i instalacja do granulacji żużla

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AT0152503A AT412650B (de) 2003-09-25 2003-09-25 Verfahren und anlage zum granulieren von schlacke
PCT/EP2004/010442 WO2005031008A1 (fr) 2003-09-25 2004-09-17 Procede et installation pour granuler des scories

Publications (3)

Publication Number Publication Date
EP1664353A1 EP1664353A1 (fr) 2006-06-07
EP1664353B1 true EP1664353B1 (fr) 2007-01-17
EP1664353B2 EP1664353B2 (fr) 2011-10-12

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP04765337A Expired - Lifetime EP1664353B2 (fr) 2003-09-25 2004-09-17 Procede et installation pour granuler des scories

Country Status (14)

Country Link
US (2) US7600397B2 (fr)
EP (1) EP1664353B2 (fr)
KR (1) KR101186277B1 (fr)
CN (1) CN1856583B (fr)
AT (2) AT412650B (fr)
AU (1) AU2004276445B2 (fr)
BR (1) BRPI0414805A (fr)
CA (1) CA2539601A1 (fr)
DE (1) DE502004002708D1 (fr)
ES (1) ES2280998T5 (fr)
PL (1) PL1664353T5 (fr)
PT (1) PT1664353E (fr)
RU (1) RU2355771C2 (fr)
WO (1) WO2005031008A1 (fr)

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KR100709061B1 (ko) * 2006-09-29 2007-04-18 주식회사 티아이엔지니어링건축사사무소 건축용 안전창호 구조
JP5303977B2 (ja) * 2008-03-20 2013-10-02 Jfeスチール株式会社 スラグの処理方法
LU91626B1 (en) * 2009-12-03 2011-06-06 Wurth Paul Sa Installation and method for processing molten material produced by a metallurgical plant, in particular for processing blast furnace slag
LU91765B1 (en) * 2010-12-14 2012-06-15 Wurth Paul Sa Steam condensation tower for a granulation installation
CN103060494B (zh) * 2013-01-09 2016-01-27 北京世纪源博科技股份有限公司 一种蒸汽回收型高炉冲渣水系统
CN103060498B (zh) * 2013-01-09 2015-03-11 北京世纪源博科技股份有限公司 一种高炉冲渣水余热发电系统
CN103555870B (zh) * 2013-10-30 2015-07-01 江苏沙钢集团有限公司 一种无冷却塔型高温炉渣水淬冷凝工艺及系统
RU2017110486A (ru) * 2014-09-21 2018-10-01 Хэтч Лтд. Газовое распыление расплавленных материалов с использованием побочных отходящих газов
CN108707709B (zh) * 2018-08-21 2023-07-25 北京京诚科林环保科技有限公司 一种高炉水渣粒化塔正压粒化装置及正压粒化方法
CN109529560A (zh) * 2018-12-27 2019-03-29 中冶京诚工程技术有限公司 一种高炉水渣系统过滤池蒸汽消白的方法

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ATE134698T1 (de) * 1991-11-29 1996-03-15 Noell En Und Entsorgungstechni Verfahren zur thermischen verwertung von abfallstoffen
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PL1664353T5 (pl) 2013-02-28
WO2005031008A1 (fr) 2005-04-07
CN1856583B (zh) 2010-12-01
RU2355771C2 (ru) 2009-05-20
KR20060093337A (ko) 2006-08-24
PT1664353E (pt) 2007-04-30
ES2280998T5 (es) 2012-02-17
US8302430B2 (en) 2012-11-06
AT412650B (de) 2005-05-25
PL1664353T3 (pl) 2007-06-29
CA2539601A1 (fr) 2005-04-07
US20090315233A1 (en) 2009-12-24
KR101186277B1 (ko) 2012-09-27
ATA15252003A (de) 2004-10-15
CN1856583A (zh) 2006-11-01
EP1664353B2 (fr) 2011-10-12
BRPI0414805A (pt) 2006-11-14
EP1664353A1 (fr) 2006-06-07
US20070107466A1 (en) 2007-05-17
US7600397B2 (en) 2009-10-13
RU2006113925A (ru) 2007-10-27
AU2004276445B2 (en) 2009-11-12
AU2004276445A1 (en) 2005-04-07
ES2280998T3 (es) 2007-09-16
ATE351927T1 (de) 2007-02-15
DE502004002708D1 (de) 2007-03-08

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