EP1224335A1 - Procede de reduction directe de materiaux contenant de l'oxyde de fer - Google Patents

Procede de reduction directe de materiaux contenant de l'oxyde de fer

Info

Publication number
EP1224335A1
EP1224335A1 EP00971317A EP00971317A EP1224335A1 EP 1224335 A1 EP1224335 A1 EP 1224335A1 EP 00971317 A EP00971317 A EP 00971317A EP 00971317 A EP00971317 A EP 00971317A EP 1224335 A1 EP1224335 A1 EP 1224335A1
Authority
EP
European Patent Office
Prior art keywords
gas
reducing gas
fluidized bed
pressure
used reducing
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.)
Withdrawn
Application number
EP00971317A
Other languages
German (de)
English (en)
Inventor
Konstantin Milionis
Gottfried Rossmann
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.)
Primetals Technologies Austria GmbH
Original Assignee
Voest Alpine Industrienlagenbau GmbH
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 Voest Alpine Industrienlagenbau GmbH filed Critical Voest Alpine Industrienlagenbau GmbH
Publication of EP1224335A1 publication Critical patent/EP1224335A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B13/00—Making spongy iron or liquid steel, by direct processes
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B13/00—Making spongy iron or liquid steel, by direct processes
    • C21B13/0033—In fluidised bed furnaces or apparatus containing a dispersion of the material
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/10—Reduction of greenhouse gas [GHG] emissions
    • Y02P10/122—Reduction of greenhouse gas [GHG] emissions by capturing or storing CO2
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/10—Reduction of greenhouse gas [GHG] emissions
    • Y02P10/134—Reduction of greenhouse gas [GHG] emissions by avoiding CO2, e.g. using hydrogen
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/10—Reduction of greenhouse gas [GHG] emissions
    • Y02P10/143—Reduction of greenhouse gas [GHG] emissions of methane [CH4]

Definitions

  • the invention relates to a process for the direct reduction of iron oxide-containing material by means of a CO and H 2 -containing reducing gas in at least one fluidized bed reduction zone, wherein CO 2 -containing used reducing gas emerging from the at least one fluidized bed reduction zone is recirculated and fresh reducing gas by CO 2 - Reforming the used reducing gas and a methane-containing gas, in particular natural gas, is produced, and a plant for carrying out the method.
  • the CO 2 then usually has to be removed from the reformed gas and the gas freed from CO 2 must be subjected to heating.
  • the advantage of the CO 2 reforming is that no CO 2 removal and no subsequent heating of the reducing gas to the desired reduction temperature are required.
  • a method is known in which iron oxide fine particles in a bubble bed and a bubble bed downstream thereof are reduced by means of a CO and H 2 -containing reducing gas, the reducing gas from the used, CO, CO 2 - And H 2 O-containing reducing gas is produced by means of CO 2 reforming.
  • the reforming and direct reduction take place at low pressures of 1.6 to 2.4 bar.
  • DE-A-195 17 766 discloses a process in which iron oxide fine particles in a plurality of circulating fluidized beds connected in series are likewise reduced by means of a CO and H 2 -containing reducing gas, fresh reducing gas as well as in DE-A-196 37 180 is produced from the used, CO-, CO 2 - and H 2 O-containing reducing gas by CO 2 reforming.
  • the invention has for its object to provide a process for the direct reduction of iron oxide-containing material in which CO and H 2 -containing reducing gas can be produced by CO 2 reforming of a methane-containing gas, in particular natural gas, and used reducing gas, but with the disadvantages of Known processes using a CO 2 reformer, such as carbon formation, deposition, large reactor diameters, etc., are to be avoided.
  • the size of a reactor accommodating the reduction zone should be kept small, but at the same time an amount of reducing gas that meets the metallurgical requirements should penetrate the reduction zone.
  • This object is achieved in that the CO 2 reforming and the direct reduction is carried out at high pressure, preferably at a pressure of at least 4 bar gauge (5 bar absolute), in particular at a pressure of about 7 bar gauge.
  • the technically sensible range for the pressure in a process of this type is 6 to 8 bar overpressure; the upper pressure limit at 15 bar overpressure
  • iron sponge produced can be fed to the briquetting by pneumatic conveyance by means of the reducing gas, so that a briquetting device serving for briquetting can be arranged next to a direct reduction device serving for direct reduction, whereby the overall height of the overall system for carrying out the method according to the invention can be kept low can be.
  • the advantage of the method according to the invention is that the CO 2 present in the used reducing gas does not have to be removed, but is used directly for the production of fresh reducing gas. Compared to known ones
  • Direct reduction processes for example according to the aforementioned US Pat. No. 5,082,251, in which the reducing gas is produced by steam reforming, the steam reformer not being connected to the reducing gas circuit, is switched by switching the CO 2 reformer in the reducing gas circuit to a lower specific reducing gas flow for the direct reduction is required, the specific reducing gas flow being understood to mean the flow of freshly supplied reducing gas based on the material to be reduced.
  • the used reducing gas is preferably at least partially subjected to a CO shift reaction before reforming. As a result, the CO is generated using water vapor according to the equation:
  • the CO portion of the gas fed to the reformer is advantageously minimized, and the CO / CO 2 ratio is set.
  • the gas ratios required for reforming and direct reduction can also be set as required, ie the CO / H 2 ratio, even in the case of a "once through" operation can be varied or the CO content reduced according to requirements.
  • the used reducing gas is compressed before reforming, preferably to a pressure of about 8 bar overpressure.
  • the waste heat from the reforming is preferably used for preheating air, H 2 O, natural gas, etc.
  • the used reducing gas is advantageously compressed before the CO shift reaction, preferably to a pressure of about 8 bar overpressure.
  • the used reducing gas is expediently heated before reforming and before the CO shift reaction which may be provided.
  • the present invention further relates to a plant for carrying out the process according to the invention, with at least one fluidized bed reactor receiving a fluidized bed reduction zone, a feed line for a CO and H 2 -containing reducing gas to the fluidized bed reactor and a gas discharge line for used reducing gas, which leads from the fluidized bed reactor to a CO 2 reformer for producing the CO- and H 2 -containing reducing gas from a methane-containing gas, in particular natural gas, and the used reducing gas, the CO 2 reformer being connected to the fluidized bed reactor via the supply line.
  • This system is characterized according to the invention in that a compression device for compressing the gas fed to the fluidized bed reactor to a high pressure, preferably to a pressure of at least 5 bar gauge, in particular to a pressure of approximately 8 bar gauge, is provided in line with the CO 2 reformer is.
  • a CO shift reactor is preferably provided in front of the CO 2 reformer for used reducing gas.
  • the supply line for water vapor can open before the CO shift reactor into a supply line for the CO 2 - and possibly CO-containing gas and / or into the CO shift reactor itself.
  • the compression device is provided for compressing the used reducing gas upstream of the CO shift reactor.
  • At least three, and particularly preferably four, fluidized bed reactors connected in series are preferably provided in the plant according to the invention.
  • the CO shift reactor can advantageously be bypassed by means of a bypass line for the used reducing gas.
  • the system according to the invention is expediently characterized by a heating device for the cleaned and compressed used reducing gas.
  • FIGS. 1 and 2 each represents a preferred embodiment of the invention, the same components being provided with the same reference numerals.
  • FIG. 1 shows four fluidized bed reactors 1 to 4 connected in series, each of which receives a stationary fluidized bed, material containing iron oxide, such as fine ore, via an ore feed line 5 to the uppermost fluidized bed reactor 4, in which heating to the reduction temperature and possibly a pre-reduction takes place. fed and then passed from fluidized bed reactor 4 to fluidized bed reactor 3, 2 and 1 via conveyor lines 6a to 6c.
  • the finished reduced material (sponge iron) is passed through a discharge line 7 and a so-called “riser” 8, which is understood to be an essentially vertical, brick-lined pipe section through which the sponge iron is pneumatically forced upwards by means of the reducing gas, a storage bunker 9 and from there a briquetting device 10, in which the sponge iron is hot briquetted.
  • a briquetting device 10 in which the sponge iron is hot briquetted.
  • the reduced material is protected against reoxidation during the briquetting by an inert gas system (not shown) or fed to an electric arc furnace located underneath.
  • the reducing gas used to convey the sponge iron through the riser 8 is drawn off via a line 11 and expanded and then fed to a further use, not shown, for example for heating purposes.
  • the use of a riser 8 has the advantage that the briquetting device 10 can be arranged next to the reduction device formed from the fluidized bed reactors 1 to 4, as a result of which the overall height of the overall system can be kept lower.
  • Another possibility (not shown) for conveying the sponge iron into the storage bunker 9 without using a Risers 8 is that the lowermost fluidized bed reactor 1 is arranged so high that the sponge iron can flow into the storage bunker 9 below it by gravity, although the disadvantage of a greater overall height of the overall system must be accepted.
  • the iron oxide-containing material Before the iron oxide-containing material is introduced into the first fluidized bed reactor 4 in the direction of flow of the material, it is subjected to a preparation treatment, not shown, such as drying.
  • Reduction gas is fed to the lowermost fluidized bed reactor 1 via a feed line 12, via lines 13a to 13c in countercurrent to the flow of the material to be reduced from fluidized bed reactor 1 to fluidized bed reactor 2, 3 and 4 and drawn off as used reducing gas via a gas discharge line 14.
  • the reducing gas flows for example at a temperature of about 800 ° C and a pressure of about 8 bar absolute in the bottom fluidized bed reactor 1 and leaves the top fluidized bed reactor 4 as a used reducing gas at a temperature of about 550 ° C and a pressure of about 6 bar absolute ,
  • the used reducing gas is cooled and washed in a cooler / cleaner 15, whereby it is freed from dust and water vapor.
  • the cooled and cleaned gas which is circulated according to the illustrated embodiments, is then fed via a line 16 to a compressor 17.
  • the used reducing gas is compressed, for example, to a pressure of approximately 8 bar.
  • a heating device 18 is provided, which serves to heat up the used reducing gas, which has been greatly cooled during cleaning by the cooler / cleaner 15, to a temperature which it requires for a CO shift reaction.
  • the consumed reducing gas thus heated is then fed via line 16a to a CO shift reactor 19, in which the CO present in the consumed reducing gas is partially converted to CO 2 and H 2 by means of water vapor.
  • water vapor is fed via a feed line 20 into line 16a, by means of which the used reducing gas is fed to the CO shift reactor 19.
  • the water vapor can also be fed directly into the CO shift reactor 19, for example.
  • the CO present in the used reducing gas is converted to CO 2 and H (partly) by means of water vapor.
  • the CO shift reactor 19 By providing the CO shift reactor 19, on the one hand, the CO content of the gas supplied to the C0 2 reformer is advantageously increased, which favors the reformer reaction, and on the other hand, the CO content is reduced, as a result of which "metal dusting", ie the destruction of metallic system parts by CO, is largely avoided.
  • the CO shift reactor 19 offers more options for setting the desired reducing gas quality.
  • the gas ratios required for reforming and direct reduction can be set as required, ie the CO / H 2 ratio can be varied or the CO content reduced according to requirements.
  • the CO shift reactor 19 can be bypassed by means of a bypass line 21, so that there is a wide variation possibility for setting the desired reducing gas quality, for example by supplying a portion of the used reducing gas directly to the CO 2 reformer 22 without passing through the CO shift reactor 19 to be directed.
  • the gas supplied via line 16b is possibly converted prior to heating together with methane-containing gas, in the example shown natural gas, supplied via line 23, CO and H 2 being formed.
  • the reformed gas leaves the CO 2 reformer, for example, at a temperature of around 930 ° C. In order to be used as a fresh reducing gas, the reformed gas must still be brought to the desired reducing gas temperature.
  • the reformed gas drawn off from the CO 2 reformer 22 via a line 12 is passed partly via a cooler 24 and partly via a line 12a bypassing the cooler with a valve 25, with a reducing gas temperature of approximately 800 ° C. is set.
  • the CO 2 reformer 22 is heated by burning natural gas, which is supplied via a line 26, with an oxygen-containing gas, such as air, which gas is supplied via a line 27.
  • an oxygen-containing gas such as air
  • Part of the used, heated reducing gas can be branched off via a line 28 and also burned with an oxygen-containing gas, such as air, for heating the CO 2 reformer 22.
  • the resulting combustion exhaust gases are drawn off from the CO 2 reformer 22 via a line 29.
  • the consumed reducing gas after heating in the heating device 18 is fed directly to the CO 2 reformer 22, which simplifies the system, but does not give the range of possibilities for the composition of the CO 2 -Reformer to influence reducing gas as in the embodiment shown in Fig. 1.
  • Composition hematite (Fe 2 O 3 ) with a pure iron content of approx. 67% grain size up to max. 12.5 mm.
  • Composition total iron content approx. 93% (Fe), metallization 92%
  • the reduced ore is conveyed via the riser 8 to the briquetting 10.
  • Dust content in the gas approx. 27 kg / t product with 9.5 g / m 3 n.
  • reducing gas scrubber 15 also referred to as a cooler / cleaner
  • Dust content 27.3 g / t product with approx. 10 mg / m 3 n.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Manufacture Of Iron (AREA)
  • Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
  • Hydrogen, Water And Hydrids (AREA)

Abstract

La présente invention concerne un procédé permettant la réduction directe de matériaux contenant de l'oxyde de fer au moyen d'un gaz réducteur contenant du CO et du H2 dans au moins une zone de réduction à lit fluidisé, le gaz réducteur utilisé sortant de la/des zone(s) de réduction et contenant du CO2 étant recyclé, et le gaz de réduction recyclé, obtenu par reformage du CO2 du gaz de réduction utilisé, et d'un gaz contenant du méthane, en particulier du gaz naturel, est produit. Dans ledit procédé, le reformage du CO2 et la réduction directe sont réalisés à une pression d'au moins 4 bar de surpression, ce qui permet d'éviter au maximum la formation de carbone et l'apparition de dépôts, et de réduire la taille du réacteur dans lequel se trouve la zone de réduction, ladite zone de réduction contenant cependant une quantité de gaz réducteur suffisante pour répondre aux exigences de métallurgie.
EP00971317A 1999-10-28 2000-10-05 Procede de reduction directe de materiaux contenant de l'oxyde de fer Withdrawn EP1224335A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
AT0181699A AT407879B (de) 1999-10-28 1999-10-28 Verfahren zur direktreduktion eisenoxidhältigen materials
AT181699 1999-10-28
PCT/EP2000/009726 WO2001031069A1 (fr) 1999-10-28 2000-10-05 Procede de reduction directe de materiaux contenant de l'oxyde de fer

Publications (1)

Publication Number Publication Date
EP1224335A1 true EP1224335A1 (fr) 2002-07-24

Family

ID=3521619

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00971317A Withdrawn EP1224335A1 (fr) 1999-10-28 2000-10-05 Procede de reduction directe de materiaux contenant de l'oxyde de fer

Country Status (8)

Country Link
EP (1) EP1224335A1 (fr)
JP (1) JP2003512532A (fr)
KR (1) KR20020045617A (fr)
AT (1) AT407879B (fr)
AU (1) AU1021301A (fr)
CA (1) CA2388847A1 (fr)
MX (1) MXPA02004227A (fr)
WO (1) WO2001031069A1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002000944A1 (fr) * 2000-06-28 2002-01-03 Voest-Alpine Industrieanlagenbau Gmbh & Co Procede et installation pour la reduction directe de minerais en particules contenant des oxydes
MXPA06003488A (es) * 2003-10-03 2006-06-08 Corus Technology Bv Metodo y aparato para reducir compuestos de metal-oxigeno.
EP2635714B1 (fr) * 2010-11-05 2017-10-18 Midrex Technologies, Inc. Appareil de tube de reformeur ayant une épaisseur de paroi variable et procédé de fabrication associé
WO2016193886A1 (fr) * 2015-05-29 2016-12-08 Szego Eduardo Luigi Procédés de synthèse d'un mélange gazeux réducteur à partir d'un flux d'hydrocarbures et de dioxyde de carbone
PL3708684T3 (pl) 2019-03-15 2022-06-20 Primetals Technologies Austria GmbH Sposób redukcji bezpośredniej w złożu fluidalnym

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Publication number Priority date Publication date Assignee Title
US3305312A (en) * 1963-03-12 1967-02-21 Exxon Research Engineering Co Synthesis process
JPS523359B1 (fr) * 1971-07-08 1977-01-27
US4265868A (en) * 1978-02-08 1981-05-05 Koppers Company, Inc. Production of carbon monoxide by the gasification of carbonaceous materials
JPS5550411A (en) * 1978-10-03 1980-04-12 Ishikawajima Harima Heavy Ind Co Ltd Direct iron manufacturing method
DE2911692A1 (de) * 1979-03-24 1980-10-02 Metallgesellschaft Ag Verfahren zur erzeugung von reduktionsgas aus festen brennstoffen
JPS57185914A (en) * 1981-05-13 1982-11-16 Kawasaki Steel Corp Fluidized reduction method for iron ore by circulation of heat medium particle and reducing gas as well as coal
US5082251A (en) * 1990-03-30 1992-01-21 Fior De Venezuela Plant and process for fluidized bed reduction of ore
US5674308A (en) * 1994-08-12 1997-10-07 Midrex International B.V. Rotterdam, Zurich Branch Spouted bed circulating fluidized bed direct reduction system and method
US6149859A (en) * 1997-11-03 2000-11-21 Texaco Inc. Gasification plant for direct reduction reactors

Non-Patent Citations (1)

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Title
See references of WO0131069A1 *

Also Published As

Publication number Publication date
ATA181699A (de) 2000-11-15
WO2001031069A1 (fr) 2001-05-03
MXPA02004227A (es) 2002-12-16
AU1021301A (en) 2001-05-08
AT407879B (de) 2001-07-25
CA2388847A1 (fr) 2001-05-03
JP2003512532A (ja) 2003-04-02
KR20020045617A (ko) 2002-06-19

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