EP0222452B1 - Procédé pour réduire le niveau d'oxydation d'oxydes métalliques - Google Patents

Procédé pour réduire le niveau d'oxydation d'oxydes métalliques Download PDF

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Publication number
EP0222452B1
EP0222452B1 EP86201942A EP86201942A EP0222452B1 EP 0222452 B1 EP0222452 B1 EP 0222452B1 EP 86201942 A EP86201942 A EP 86201942A EP 86201942 A EP86201942 A EP 86201942A EP 0222452 B1 EP0222452 B1 EP 0222452B1
Authority
EP
European Patent Office
Prior art keywords
fluidized bed
supplied
metal oxides
solids
reduction
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP86201942A
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German (de)
English (en)
Other versions
EP0222452A1 (fr
Inventor
Martin Hirsch
Hermann Lommert
Harry Dr. Serbent
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.)
GEA Group AG
Original Assignee
Metallgesellschaft AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Metallgesellschaft AG filed Critical Metallgesellschaft AG
Publication of EP0222452A1 publication Critical patent/EP0222452A1/fr
Application granted granted Critical
Publication of EP0222452B1 publication Critical patent/EP0222452B1/fr
Expired legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B47/00—Obtaining manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/02—Obtaining nickel or cobalt by dry processes
    • C22B23/023—Obtaining nickel or cobalt by dry processes with formation of ferro-nickel or ferro-cobalt
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B5/00—General methods of reducing to metals
    • C22B5/02—Dry methods smelting of sulfides or formation of mattes
    • C22B5/10—Dry methods smelting of sulfides or formation of mattes by solid carbonaceous reducing agents
    • 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
    • Y10S423/00—Chemistry of inorganic compounds
    • Y10S423/09—Reaction techniques
    • Y10S423/16—Fluidization

Definitions

  • the invention relates to a method for reducing higher metal oxides to lower metal oxides by means of carbon-containing reducing agents.
  • ores that contain metals - such as Fe, Ni, Mn - in the form of higher oxides have to be subjected to a reducing treatment so that these metals are in the form of lower oxides.
  • ferroalloys While e.g. in the case of an ore with 30% Fe and 2% Ni, an Fe / Ni ratio of 15/1 is present, commercially available ferroalloys have such ratios of at most 4/1, i.e. their nickel content is at least 20%.
  • Such ores are processed in such a way that they are reduced as far as possible to the FeO stage by means of a pre-reduction and then only as much metallic iron is produced in a melting process by further reduction as is permissible for the desired ferroalloy.
  • the remaining iron oxide is slagged.
  • the pre-reduction is carried out on an industrial scale in rotary kilns using coal as a reducing agent.
  • the problem of the pre-reduction in the rotary kiln lies in the constant adherence to an exact pre-reduction of the iron oxides, the discharge material being allowed to contain only as much excess, solid carbon as is permissible for the further reduction in the melting process.
  • Another case of using the method according to the invention relates to the reduction of ores which contain higher manganese oxides and whose manganese content is to be reduced to low manganese oxides.
  • the object of the invention is to carry out the reduction of higher metal oxides to lower metal oxides as largely and constantly as possible to the desired oxidation state and to set either as little or a constant, small excess of carbon in the reduced discharge material.
  • the grain size of the solids is in the range of less than 3 mm.
  • the calcination can take place in a stationary fluidized bed, a circulating fluidized bed or another process in which the solids are suspended in a gas stream.
  • the raw materials can be dried in the calcination before use. Drying can take place with the waste heat from the calcination. As a result, the water is evaporated without the consumption of carbon, the water vapor does not have to be heated to the considerably higher temperature in the calcination, and the waste heat is used in a favorable manner. After drying, further heating can be carried out before charging into the calcination, a certain amount of precalculation being able to occur.
  • a stationary fluidized bed is to be understood as a fluidized bed in which a dense phase is separated from the dust space above by a clear density jump, and a defined boundary layer exists between these two distribution states.
  • the amount of the oxygen-containing gases passed as a fluidizing gas into the stationary fluidized bed is such that the carbon-containing reducing agent is either virtually completely gasified or gasified to a desired excess of carbon in the discharge material.
  • the oxygen-containing gases generally consist of air.
  • a preferred embodiment consists in that the calcination according to (a) takes place in a circulating fluidized bed, the suspension discharged from the fluidized bed reactor is passed into a separator, at least a partial stream of the separated solids is returned to the fluidized bed reactor, and the exhaust gas for drying and preheating the solids containing higher metal oxides are passed into suspension heat exchangers.
  • the circulating fluidized bed system consists of a fluidized bed reactor, a separator and a return line for solids from the separator to the fluidized bed reactor.
  • the fluidized bed in the fluidized bed reactor has - in contrast to the stationary fluidized bed, in which a dense phase is separated from the gas space above by a clear density jump - distribution states without a defined boundary layer.
  • the solids discharged from the fluidized bed reactor with the gases are returned to the fluidized bed reactor to form a circulating fluidized bed such that the hourly solids circulation is at least five times the solids weight in the reactor shaft matters.
  • a quantity of solids corresponding to the entry is withdrawn from the system of the circulating fluidized bed and passed into the stationary fluidized bed.
  • the circulating fluidized bed results in a high throughput during calcination, a high burnout of the fuel and, due to the multi-stage combustion, a low content of CO and NO x in the exhaust gas.
  • a preferred embodiment consists in that the exhaust gas from the stationary fluidized bed according to (d) is passed through a separator before being introduced into the calcination, and the separated solid is returned to the stationary fluidized bed.
  • the dust separator expediently consists of a cyclone. This largely avoids the circulation of solids between the reduction stage and the oxidation stage.
  • a preferred embodiment is that the reduction according to (b) is carried out with the addition of solid, carbon-containing reducing agents.
  • the addition of solid fuels results in a better distribution in the fluidized bed and the desired amount of excess carbon in the discharge material can be adjusted very precisely and evenly.
  • One embodiment consists of the use of iron-nickel ores and the addition of carbon-containing reducing agent in the stationary fluidized bed in accordance with (c) such that it is used to reduce the higher iron oxides, for example to the FeO stage, to reduce the nickel oxides, is sufficient to set the reduction temperature and there is a maximum of 2% by weight of excess carbon in the discharge material, and the discharge material is further processed in the melt flow to produce an amount of metallic iron corresponding to the desired iron-nickel alloy and slagging of the remaining iron content.
  • One embodiment consists in that materials containing manganese oxides are used, and the addition of carbon-containing reducing agent in the stationary fluidized bed is dimensioned in accordance with (c) such that it is sufficient to reduce the higher manganese oxides, for example to the MnO stage, to set the reduction temperature, and There is as little excess carbon as possible in the discharge material.
  • the ore 1 is charged via a screw 2 into a venturi-like suspension dryer 3. There it is suspended in the gas stream and passed via line 4 into a separator 5. The gas is cleaned in the electrostatic filter 6 and discharged as exhaust gas 7. The separated solids are fed into line 8 by screw 7a. A partial stream is fed into the calcination via line 9.
  • the calcination is designed as a circulating fluidized bed and consists of the fluidized bed reactor 10, the recycle cyclone 11 and the recycle line 12. A part of the solid is passed via line 13 into the preheater 14, suspended there in the gas stream and passed via line 15 into the separator 16. The separated solid is passed into the reactor 10 via line 17. The gas flows from the separator 16 into the suspension dryer 3.
  • Fluidizing air 18 is introduced into the lower region of the reactor 10. At a higher point, secondary air 19 and coal 20 are introduced.
  • a gas / solid suspension which fills the entire reactor 10 is formed within the fluidized bed reactor 10 and is passed at the top via line 21 into the recycling cyclone 11, where a separation of solid and gas takes place.
  • the gas flows into the preheater 14 and the solid enters the return line 12, in which a U-shaped closure 13 is arranged, in the bottom of which a small amount of fluidizing air (not shown) is passed.
  • Part of the calcined solid passes from the closure 13 via a controllable valve 22 and line 23 into the stationary fluidized bed 24, in which the reduction takes place. Fluidizing air is blown into the lower part via line 25 and coal is introduced via line 26.
  • the dust-containing exhaust gas is passed via line 27 into the separator 28.
  • the separated solids return to the stationary fluidized bed 24 via line 29, while the exhaust gas is introduced via line 30 into the fluidized bed reactor 10 at a higher point.
  • the reduced material is discharged via line 31.
  • Calcined solids can also be fed into the stationary fluidized bed 24 via line 32.
  • the fluidized bed reactor 10 has a diameter of 3.7 m and a height of 16 m.
  • the temperature in the reactor is 900 ° C.
  • the fluidized bed reactor 24 has a diameter of 3 m and a height of 2.5 m.
  • the temperature in the reactor is 900 ° C.
  • the advantages of the invention are that, on the one hand, the calcination can be carried out in a very economical manner with the generation of a largely burnt-out, low-pollutant exhaust gas and, on the other hand, a reduced product is obtained which has a precise and uniform degree of reduction and a precisely defined and uniform content of excess Contains carbon, which content can also be practically zero.
  • the iron oxides can be largely reduced to FeO and the formation of metallic iron can nevertheless be avoided.
  • the carbon content in the discharge can be kept very low or only as high and absolutely uniform as is necessary for the reduction of the small amounts of metallic iron in the melting process. This enables precise metering of the amount of carbon in the electric furnace.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Oxygen, Ozone, And Oxides In General (AREA)

Claims (6)

1. Procédé de réduction d'oxydes métalliques à degré d'oxydation élevé en oxydes métalliques à degrés d'oxydation plus bas, qui consiste
a) à calciner dans un premier réacteur (10) des substances solides sous forme de grains fins contenant des oxydes métalliques à degré d'oxydation élevé, au moyen de gaz chauds, en opérant entre 800 et 1100°C, les matières solides étant en suspension dans les gaz chauds,
b) ensuite, dans un autre réacteur ayant un lit fluidisé (24) fixe, à réduire les matières solides calcinées, par addition d'agents réducteurs carbonés et de gaz contenant de l'oxygène, en oxydes métalliques à degré d'oxydation plus bas, en opérant à une température comprise entre 800 et 1100°C,
c) à proportionner l'addition d'agent réducteur carboné dans (b) de façon que la quantité de carbone, ajoutée pour réduire les oxydes métalliques à degré d'oxydation élevé en oxydes métalliques à degré d'oxydation plus bas, suffise à produire la température de réduction et à régler la teneur souhaitée en carbone du matériau déchargé,
d) à envoyer l'effluent gazeux du lit fluidisé fixe suivant (b), à titre de gaz secondaire, à la calcination suivant (a), et
e) à envoyer à la calcination suivant (a) du combustible en une quantité telle que sa combustion et la quantité de chaleur introduite par l'effluent gazeux suivant (d) donnent la quantité de chaleur nécessaire à la calcination.
2. Procédé suivant la revendication 1, caractérisé en ce qu'il consiste à effectuer la calcination suivant (a) dans un lit fluidisé circulant, à envoyer la suspension déchargée du réacteur à lit fluidisé dans un séparateur, à retourner au moins un courant partiel de la matière solide séparée au réacteur à lit fluidisé, et à envoyer l'effluent gazeux dans l'échangeur de chaleur de suspension pour le séchage et pour le préchauffage des matières solides contenant les oxydes métalliques à degré d'oxydation élevé.
3. Procédé suivant la revendication 1 ou 2, caractérisé en ce qu'il consiste à envoyer l'effluent gazeux du lit fluidisé fixe suivant (d), avant de l'envoyer à la calcination, dans un séparateur et à retourner la matière solide séparée au lit fluidisé fixe.
4. Procédé suivant l'une des revendications 1 à 3, caractérisé en ce qu'il consiste à effectuer la réduction suivant (b) par addition d'agents réducteurs solides carbonés.
5. Procédé suivant l'une des revendications 1 à 4, caractérisé en ce qu'il consiste à mettre en oeuvre du minerai de fer et de nickel et à proportionner l'addition d'agent réducteur carboné dans le lit fluidisé fixe suivant (c), de sorte qu'elle suffise à la réduction des oxydes de fer à degré d'oxydation élevé, à peu près jusqu'au stade de FeO, à la réduction des oxydes de nickel et au réglage de la température de réduction et qu'il y ait, dans le matériau déchargé, une teneur en carbone en excès de 2% en poids au maximum, et à traiter ensuite le matériau déchargé à l'état fondu avec production d'une quantité de fer métallique correspondant à l'alliage de fer et de nickel souhaité, et avec scorification de la teneur résiduelle en fer.
6. Procédé suivant l'une des revendications 1 à 4, caractérisé en ce qu'il consiste à utiliser des matériaux contenant de l'oxyde de manganèse, et à proportionner l'addition d'agent réducteur carboné au lit fluidise fixe suivant (c), de façon qu'elle suffise à la réduction des oxydes de manganèse ayant un degré d'oxydation élevé, à peu près au stade de MnO, et au réglage de la température de réduction, et à ce qu'il y ait, dans le matériau déchargé, aussi peu que possible de carbone en excès.
EP86201942A 1985-11-15 1986-11-07 Procédé pour réduire le niveau d'oxydation d'oxydes métalliques Expired EP0222452B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19853540541 DE3540541A1 (de) 1985-11-15 1985-11-15 Verfahren zur reduktion von hoeheren metalloxiden zu niedrigen metalloxiden
DE3540541 1985-11-15

Publications (2)

Publication Number Publication Date
EP0222452A1 EP0222452A1 (fr) 1987-05-20
EP0222452B1 true EP0222452B1 (fr) 1989-04-05

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Application Number Title Priority Date Filing Date
EP86201942A Expired EP0222452B1 (fr) 1985-11-15 1986-11-07 Procédé pour réduire le niveau d'oxydation d'oxydes métalliques

Country Status (10)

Country Link
US (1) US4789580A (fr)
EP (1) EP0222452B1 (fr)
AU (1) AU588647B2 (fr)
BR (1) BR8605633A (fr)
CA (1) CA1266368A (fr)
DE (2) DE3540541A1 (fr)
GR (2) GR880300159T1 (fr)
IN (1) IN166635B (fr)
NO (1) NO169499C (fr)
NZ (1) NZ217937A (fr)

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FI84841C (sv) * 1988-03-30 1992-01-27 Ahlstroem Oy Förfarande och anordning för reduktion av metalloxidhaltigt material
ZA946071B (en) * 1993-08-30 1995-03-16 Mintek The production of ferronickel from nickel containing laterite
RU2044088C1 (ru) * 1994-04-15 1995-09-20 Акционерное общество закрытого типа "ККИП" Способ извлечения марганца из марганецсодержащего сырья
CH689633A5 (de) * 1995-01-10 1999-07-30 Von Roll Umwelttechnik Ag Verfahren zur Kuehlung und Reinigung von Rauchgasen.
CU23070A3 (es) 1999-01-12 2005-07-19 Falconbridge Ltd Reduccion de la capa fludizada de finos de laterita con reduccion de gases generados in situ.
DE10101157A1 (de) * 2001-01-12 2002-07-18 Mg Technologies Ag Verfahren zum Erzeugen eines Gemisches aus Eisenerz und Schwelkoks
DE10260733B4 (de) * 2002-12-23 2010-08-12 Outokumpu Oyj Verfahren und Anlage zur Wärmebehandlung von eisenoxidhaltigen Feststoffen
DE10260738A1 (de) * 2002-12-23 2004-07-15 Outokumpu Oyj Verfahren und Anlage zur Förderung von feinkörnigen Feststoffen
DE10260734B4 (de) * 2002-12-23 2005-05-04 Outokumpu Oyj Verfahren und Anlage zur Herstellung von Schwelkoks
DE10260741A1 (de) 2002-12-23 2004-07-08 Outokumpu Oyj Verfahren und Anlage zur Wärmebehandlung von feinkörnigen Feststoffen
DE10260737B4 (de) * 2002-12-23 2005-06-30 Outokumpu Oyj Verfahren und Anlage zur Wärmebehandlung von titanhaltigen Feststoffen
DE10260731B4 (de) * 2002-12-23 2005-04-14 Outokumpu Oyj Verfahren und Anlage zur Wärmebehandlung von eisenoxidhaltigen Feststoffen
DE10260739B3 (de) * 2002-12-23 2004-09-16 Outokumpu Oy Verfahren und Anlage zur Herstellung von Metalloxid aus Metallverbindungen
DE102004042430A1 (de) * 2004-08-31 2006-03-16 Outokumpu Oyj Wirbelschichtreaktor zum thermischen Behandeln von wirbelfähigen Substanzen in einem mikrowellenbeheizten Wirbelbett
US9371487B2 (en) * 2007-12-12 2016-06-21 Outotec Oyj Process and plant for producing char and fuel gas
CN102851490B (zh) * 2012-08-30 2014-04-16 北京矿冶研究总院 流态化还原焙烧氧化镍矿制备优质焙砂的方法
CN104911332B (zh) * 2015-05-07 2017-04-05 王立臣 一种低品位氧化锰矿分段立式焙烧炉装置及其使用方法
JP7147409B2 (ja) * 2018-09-20 2022-10-05 住友金属鉱山株式会社 酸化鉱石の製錬方法
RU2721249C1 (ru) * 2019-11-29 2020-05-18 Валентин Николаевич Терехов Состав шихты для выплавки безуглеродистого железа

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Also Published As

Publication number Publication date
BR8605633A (pt) 1987-08-18
AU588647B2 (en) 1989-09-21
EP0222452A1 (fr) 1987-05-20
NO169499C (no) 1992-07-01
DE3662700D1 (en) 1989-05-11
GR3000079T3 (en) 1990-10-31
GR880300159T1 (en) 1989-03-08
NO169499B (no) 1992-03-23
DE3540541A1 (de) 1987-05-21
IN166635B (fr) 1990-06-30
NO864490D0 (no) 1986-11-11
NZ217937A (en) 1989-07-27
NO864490L (no) 1987-05-18
US4789580A (en) 1988-12-06
CA1266368A (fr) 1990-03-06
AU6513486A (en) 1987-05-21

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