EP0766747A1 - Verfahren zur direktreduktion von eisenoxidhältigem material - Google Patents

Verfahren zur direktreduktion von eisenoxidhältigem material

Info

Publication number
EP0766747A1
EP0766747A1 EP95919926A EP95919926A EP0766747A1 EP 0766747 A1 EP0766747 A1 EP 0766747A1 EP 95919926 A EP95919926 A EP 95919926A EP 95919926 A EP95919926 A EP 95919926A EP 0766747 A1 EP0766747 A1 EP 0766747A1
Authority
EP
European Patent Office
Prior art keywords
gas
line
direct reduction
reducing
reducing gas
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.)
Ceased
Application number
EP95919926A
Other languages
German (de)
English (en)
French (fr)
Inventor
Roland Fluch
Karl Czermak
Günter PEER
Roy Hubert Whipp, Jr.
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
Brifer International Ltd
Original Assignee
Voest Alpine Industrienlagenbau GmbH
Brifer International Ltd
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, Brifer International Ltd filed Critical Voest Alpine Industrienlagenbau GmbH
Publication of EP0766747A1 publication Critical patent/EP0766747A1/de
Ceased legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21BMANUFACTURE OF IRON OR STEEL
    • C21B13/00Making spongy iron or liquid steel, by direct processes
    • C21B13/0073Selection or treatment of the reducing gases
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21BMANUFACTURE OF IRON OR STEEL
    • C21B2100/00Handling of exhaust gases produced during the manufacture of iron or steel
    • C21B2100/20Increasing the gas reduction potential of recycled exhaust gases
    • C21B2100/22Increasing the gas reduction potential of recycled exhaust gases by reforming
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21BMANUFACTURE OF IRON OR STEEL
    • C21B2100/00Handling of exhaust gases produced during the manufacture of iron or steel
    • C21B2100/20Increasing the gas reduction potential of recycled exhaust gases
    • C21B2100/28Increasing the gas reduction potential of recycled exhaust gases by separation
    • C21B2100/282Increasing the gas reduction potential of recycled exhaust gases by separation of carbon dioxide
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21BMANUFACTURE OF IRON OR STEEL
    • C21B2100/00Handling of exhaust gases produced during the manufacture of iron or steel
    • C21B2100/60Process control or energy utilisation in the manufacture of iron or steel
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/10Reduction of greenhouse gas [GHG] emissions
    • Y02P10/122Reduction of greenhouse gas [GHG] emissions by capturing or storing CO2
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/10Reduction of greenhouse gas [GHG] emissions
    • Y02P10/134Reduction of greenhouse gas [GHG] emissions by avoiding CO2, e.g. using hydrogen
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/10Reduction of greenhouse gas [GHG] emissions
    • Y02P10/143Reduction of greenhouse gas [GHG] emissions of methane [CH4]

Definitions

  • the invention relates to a process for the direct reduction of iron oxide-containing material, synthesis gas, preferably reformed natural gas, being mixed with top gas formed in the direct reduction of the iron oxide-containing material and used as a reducing gas for direct reduction and for heating the iron oxide-containing material to the reduction temperature, and a system for carrying out the Procedure.
  • Metal dusting occurs increasingly at higher temperatures, which means in particular Parts of the system that come into contact with hot reducing gas are at risk.
  • these are, in particular, the reactors used for direct reduction and the gas heater which heats the reducing gas to the reduction temperature.
  • the invention aims to avoid these disadvantages and difficulties and has as its object to provide a method of the type described above and a system for carrying out the method, which an adjustment of an H2S content to a predetermined value with sufficient accuracy and avoiding a large enable procedural or constructive and costly effort.
  • This object is achieved in that at least part of a sulfur contained in the iron oxide-containing material in the form of H2S obtained during the heating or the direct reduction is fed to the reducing gas with the top gas.
  • the invention is based on the idea of utilizing the sulfur usually contained in the ore, which has hitherto not been used in further processing, and makes the fact take advantage of the fact that when sulfur-containing ore is heated, H2S is formed.
  • this PbS is derived as the top gas with the reducing gas which brings about the heating and from which it is absorbed, and is fed to the reducing gas.
  • a __2S content in the reducing gas is expediently set in the size of 20 to 40 ppmV, preferably in the size of approximately 25 ppmV, with the top gas.
  • the top gas is subjected to a CO 2 scrubbing before use as a reducing gas, and the __2S content in the reducing gas is adjusted by admixing at least a partial volume of the top gas to the reducing gas bypassing the CO 2 scrubbing.
  • This variant is particularly easy to implement, since only a bypass line which bridges the CO 2 washer is to be arranged. This prevents the FbS present in this part of the top gas from being washed out, whereas the remaining part of the top gas is subjected to an Olb wash, in which H2S is also washed out.
  • the desired H2S content of the reducing gas can be set in a simple manner by varying the amount of top gas passed through the bypass line.
  • a further preferred embodiment is characterized in that reformed natural gas is used as synthesis gas and that both the reformed natural gas and the top gas are subjected to a CO 2 scrubbing before use as a reducing gas, a partial volume of the reformed natural gas being bypassed by the CO 2 scrubbing Reducing gas is added directly.
  • a desired CO content can be set in a simple manner or changes in the CO 2 content and the CO / CO2 ratio of the reducing gas caused by the direct admixing of a part of a CO2-unwashed top gas can be compensated for, taking into account the desired H2S content.
  • Another preferred possibility for setting the desired H2S content in the reducing gas is characterized in that the setting of the H2S content in the reducing gas is carried out by varying the degree of washing out of the CO 2 wash, etc. in that part of the CO2 and thus part of the H2S remain in the scrubbed gas.
  • This embodiment requires the least possible design effort, that is, not even the arrangement of a bypass line, but it must be taken into account that the entire gas must be passed through the CO2 scrubber, which must be dimensioned accordingly
  • the particulate iron oxide-containing material is preferred in the event that it is not sulfur-containing. a sulfur-containing material such as Fe pyrite is added, thereby causing the formation of H2S and its inclusion in the reducing gas which brings about the heating of the iron oxide-containing material to the reduction temperature.
  • a reformer for reforming natural gas and a reforming gas line starting from the reformer, which opens together with the top gas discharge line, are provided for producing the synthesis gas, both the reformed gas line and the top gas discharge line opening into the b scrubber.
  • the bypass line of the reformed gas line is preferably connected to the reducing gas supply line bypassing the CO 2 scrubber by means of a bypass line.
  • the bypass line (s) is (are) suitably equipped with a control valve, preferably a control valve, which can be activated via an H2S measuring device.
  • the plant according to the invention has four fluidized bed reactors 1 to 4 connected in series, with iron oxide-containing material, such as fine ore, being fed via an ore feed line 5 to the first fluidized bed reactor 1, in which the heating to the reduction temperature (or a pre-reduction) takes place, and then from Fluidized bed reactor to fluidized bed reactor via feed lines 6 is passed.
  • the finished reduced material (sponge iron) is hot briquetted in a briquetting system 7 If necessary, the reduced iron is protected from reoxidation by an inert gas system (not shown) during the briquetting.
  • the fine ore Before the fine ore is introduced into the first fluidized bed reactor 1, it is subjected to an ore preparation, such as drying and sieving, which is not shown in detail.
  • Reducing gas is conducted in countercurrent to the ore flow from the fluidized bed reactor 4 to the fluidized bed reactor 3 to 1 and is discharged as top gas via a top gas discharge line 8 from the last fluidized bed reactor 1 in the gas flow direction and cooled and washed in a wet scrubber 9.
  • the reduction gas is produced by reforming natural gas supplied via line 11 and desulfurized in a desulfurization system 12 in a reformer 10.
  • the gas formed from natural gas and steam and leaving reformer 10 essentially consists of H2, CO, CH4, H2O and CO2 .
  • This reformed natural gas is fed via the reformed gas line 13 to a plurality of heat exchangers 14, in which it is cooled, as a result of which water is condensed out of the gas.
  • the reformed gas line 13 opens into the top gas discharge line 8 after the top gas has been compressed by means of a compressor 15.
  • the mixed gas thus formed is sent through a CO2 scrubber 16 and freed of CO2 and thereby also of H2S. It is now available as a reducing gas.
  • This reducing gas is heated via a reducing gas feed line in a gas heater 18 arranged downstream of the CO 2 scrubber 16 to a reducing gas temperature of approximately 800 ° C. and fed to the first fluidized bed reactor 4 in the gas flow direction, where it reacts with the fine ores to produce direct-reduced iron.
  • the fluidized bed reactors 4 to 1 are connected in series; the reducing gas passes through the connecting lines 19 from the fluidized bed reactor to the fluidized bed reactor.
  • Part of the top gas is removed from the gas circuit 8, 17, 19 in order to avoid an enrichment of inert gases, such as N2.
  • the discharged top gas is fed via a branch line 20 to the gas heater 18 for heating the reducing gas and burned there. Any missing energy is supplemented by natural gas which is fed in via the feed line 21
  • the sensible heat of the reformed natural gas emerging from the reformer 10 and of the reformer fumes is used in a recuperator 22 to preheat the natural gas after passing through the desulfurization system 12, to generate the steam required for the reforming and to supply the gas heater 18 via line 23 Preheat the combustion air and possibly also the reducing gas.
  • the combustion air supplied to the reformer via line 24 is also preheated.
  • the top gas leaving the fluidized bed reactor 1 has - depending on the sulfur content of the ore - an H2S content of 40 to 140 ppmV.
  • the H2S gas forms during the heating of the fine ore to the reduction temperature or during the pre-reduction of the fine ore.
  • the H2S is no longer completely washed out of the top gas by means of the CO 2 scrubber, but care is taken to ensure that the percentage of H2S of the top gas desired for the reducing gas is fed to the reducing gas.
  • this can be achieved by means of a bypass line 25 which bypasses the CO 2 scrubber 16, which starts from the top gas discharge line 8 via a control or regulating valve 26 and opens into the reducing gas supply line 17.
  • the control or regulating valve 26 can be set such that an H2S content in the reducing gas in the size of 20 to 40 ppmV, preferably in the size of about 25 ppmV. is available.
  • the control valve 26 is preferably activated via an H2S measuring device 27, not shown.
  • the desired H2S content in the reducing gas can also be set by passing all of the top gas through the C02 scrubber 16, but this is set to a degree of leaching at which part of the CO2 and thus part of the H2S is removed the gas emerging from the CO 2 scrubber 16 remain.
  • This has the advantage that no auxiliary devices, such as a bypass line 25 with control valve 26, have to be provided, but requires that the entire gas quantity, that is to say the entire top gas and the entire reformed natural gas, must be passed through the CO 2 scrubber 16 , so that this must be measured for this amount.
  • a part can be used to set a desired CO 2 content or a desired CO / CO2 ratio, which is influenced by a change in the degree of scrubbing of the CO 2 scrubber 16 or by a direct supply of part of the top gas via the bypass line 25 of the reformed natural gas are fed to the reducing gas supply line 17 via a bypass line 29 bridging the CO2 scrubber 16 and also equipped with an adjustable valve 28; this bypass line 29 then goes from the Reform gas line 13 out.
  • the measures described above for setting a desired H2S content in the reducing gas can be implemented individually or together.
  • the reformed natural gas and the top gas have the chemical composition given in the table below:
  • the gas mixture emerging from the CO 2 scrubber 16 and formed from the scrubbed reformed natural gas and the scrubbed top gas is composed as follows:
  • This gas mixture is mixed with 78,000 N ⁇ vVh of the top gas which was not passed through the CO 2 scrubber 16.
  • This gas mixture forms the reducing gas which is fed to the gas heater 18 and subsequently to the fluidized bed reactors 1 to 4 and has the following chemical composition:
  • the degree of metallization of the sponge iron is 92 9c.
  • the reformed natural gas and the top gas have the chemical composition given in the table below:
  • the gas mixture emerging from the CO 2 scrubber 16 and formed from the washed reformed natural gas and the top gas is composed as follows:
  • This gas mixture is mixed with 94,000 Nm 3 / h of the top gas which was not passed through the CO 2 scrubber 16.
  • This gas mixture forms the reducing gas fed to the gas heater 18 and subsequently to the fluidized bed reactors 1 to 4 and has the following chemical composition:
  • the degree of metallization of the sponge iron is 92 9c.
  • the invention is not limited to the examples described above, but is also used for other direct reduction processes, e.g. those in which 1 to 4 shaft furnaces for lump ore are used instead of the fluidized bed reactors can be used.
  • other reducing gases containing mainly CO and H2 such as

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Iron (AREA)
  • Catalysts (AREA)
  • Manufacture And Refinement Of Metals (AREA)
EP95919926A 1994-06-23 1995-06-20 Verfahren zur direktreduktion von eisenoxidhältigem material Ceased EP0766747A1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
AT0124894A AT402825B (de) 1994-06-23 1994-06-23 Verfahren zur direktreduktion von eisenoxidhältigem material
AT1248/94 1994-06-23
PCT/AT1995/000121 WO1996000302A1 (de) 1994-06-23 1995-06-20 Verfahren zur direktreduktion von eisenoxidhältigem material

Publications (1)

Publication Number Publication Date
EP0766747A1 true EP0766747A1 (de) 1997-04-09

Family

ID=3509806

Family Applications (1)

Application Number Title Priority Date Filing Date
EP95919926A Ceased EP0766747A1 (de) 1994-06-23 1995-06-20 Verfahren zur direktreduktion von eisenoxidhältigem material

Country Status (14)

Country Link
US (1) US5871560A (xx)
EP (1) EP0766747A1 (xx)
JP (1) JP3248915B2 (xx)
KR (1) KR100240811B1 (xx)
AT (1) AT402825B (xx)
AU (1) AU691293B2 (xx)
BR (1) BR9508108A (xx)
CA (1) CA2193855C (xx)
MX (1) MX9606728A (xx)
PE (1) PE49695A1 (xx)
RU (1) RU2125098C1 (xx)
UA (1) UA27080C2 (xx)
WO (1) WO1996000302A1 (xx)
ZA (1) ZA955177B (xx)

Families Citing this family (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6136019A (en) * 1996-08-19 2000-10-24 Mower Family Chf Treatment Irrevocable Trust Augmentation of electrical conduction and contractility by biphasic cardiac pacing administered via the cardiac blood pool
US7908003B1 (en) 1996-08-19 2011-03-15 Mr3 Medical Llc System and method for treating ischemia by improving cardiac efficiency
US8447399B2 (en) * 1996-08-19 2013-05-21 Mr3 Medical, Llc System and method for managing detrimental cardiac remodeling
US7440800B2 (en) * 1996-08-19 2008-10-21 Mr3 Medical, Llc System and method for managing detrimental cardiac remodeling
AT406382B (de) * 1996-11-06 2000-04-25 Voest Alpine Ind Anlagen Verfahren zum herstellen von eisenschwamm durch direktreduktion von eisenoxidhältigem material
AUPO426096A0 (en) 1996-12-18 1997-01-23 Technological Resources Pty Limited Method and apparatus for producing metals and metal alloys
AUPO426396A0 (en) 1996-12-18 1997-01-23 Technological Resources Pty Limited A method of producing iron
US6149859A (en) 1997-11-03 2000-11-21 Texaco Inc. Gasification plant for direct reduction reactors
AUPP554098A0 (en) 1998-08-28 1998-09-17 Technological Resources Pty Limited A process and an apparatus for producing metals and metal alloys
AUPQ152299A0 (en) 1999-07-09 1999-08-05 Technological Resources Pty Limited Start-up procedure for direct smelting process
AUPQ205799A0 (en) * 1999-08-05 1999-08-26 Technological Resources Pty Limited A direct smelting process
AUPQ213099A0 (en) 1999-08-10 1999-09-02 Technological Resources Pty Limited Pressure control
AUPQ308799A0 (en) 1999-09-27 1999-10-21 Technological Resources Pty Limited A direct smelting process
AUPQ346399A0 (en) 1999-10-15 1999-11-11 Technological Resources Pty Limited Stable idle procedure
AUPQ365799A0 (en) 1999-10-26 1999-11-18 Technological Resources Pty Limited A direct smelting apparatus and process
US6602321B2 (en) 2000-09-26 2003-08-05 Technological Resources Pty. Ltd. Direct smelting process
KR100445835B1 (ko) * 2001-05-25 2004-08-25 한국타이어 주식회사 타이어 트레드용 고무 조성물
KR20030037530A (ko) * 2001-11-06 2003-05-14 박재석 일회용 전분제 용기 및 그 제조방법
UA97275C2 (ru) * 2007-05-25 2012-01-25 Хил ТЕЧНОЛОДЖИС, С.А. ГДЕ К.В. СПОСОБ ПРОИЗВОДСТВА ЖЕЛЕЗА ПРЯМОГО ВОССТАНОВЛЕНИЯ В восстановительном РЕАКТОРе
EP2209922A2 (en) * 2007-11-20 2010-07-28 Shell Internationale Research Maatschappij B.V. Process for production of elemental iron
CN109868335B (zh) * 2019-03-19 2021-01-26 重庆大学 一种闭环利用铁矿石还原过程中尾气的系统及方法

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GB799551A (en) * 1956-02-06 1958-08-13 Texaco Development Corp Reduction of a metal oxide with carbon monoxide and hydrogen
US3377156A (en) * 1965-07-30 1968-04-09 Exxon Research Engineering Co Process of reducing iron oxide ores with gases containing carbon monoxide
US3936296A (en) * 1970-02-25 1976-02-03 Campbell Donald L Integrated fluidized reduction and melting of iron ores
DE2907022A1 (de) * 1979-02-23 1980-08-28 Maschf Augsburg Nuernberg Ag Tiefkuehl-aufbereitung von rohgas aus der kohlevergasung zur verwendung bei der direktreduktion
US4333761A (en) * 1979-10-22 1982-06-08 Midrex Corporation Method for direct reduction of iron using high sulfur gas
JPS5811484B2 (ja) * 1980-12-04 1983-03-03 三菱重工業株式会社 還元鉄の製造方法
AT402937B (de) * 1992-05-22 1997-09-25 Voest Alpine Ind Anlagen Verfahren und anlage zur direktreduktion von teilchenförmigem eisenoxidhältigem material
US5531424A (en) * 1993-04-19 1996-07-02 Fior De Venezuela Fluidized bed direct reduction plant

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Also Published As

Publication number Publication date
JPH10505634A (ja) 1998-06-02
CA2193855A1 (en) 1996-01-04
US5871560A (en) 1999-02-16
KR100240811B1 (ko) 2000-01-15
AT402825B (de) 1997-09-25
AU2556895A (en) 1996-01-19
AU691293B2 (en) 1998-05-14
RU2125098C1 (ru) 1999-01-20
CA2193855C (en) 2001-09-18
BR9508108A (pt) 1997-08-12
UA27080C2 (uk) 2000-02-28
ZA955177B (en) 1996-01-31
JP3248915B2 (ja) 2002-01-21
MX9606728A (es) 1997-04-30
PE49695A1 (es) 1996-01-22
WO1996000302A1 (de) 1996-01-04
ATA124894A (de) 1997-01-15

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