EP1753884A1 - Pierre agglomeree pour fours a cuve, fours corex et hauts fourneaux, procede pour fabriquer cette pierre agglomeree et utilisation de poussieres de minerai de fer fines et hyperfines - Google Patents

Pierre agglomeree pour fours a cuve, fours corex et hauts fourneaux, procede pour fabriquer cette pierre agglomeree et utilisation de poussieres de minerai de fer fines et hyperfines

Info

Publication number
EP1753884A1
EP1753884A1 EP05745341A EP05745341A EP1753884A1 EP 1753884 A1 EP1753884 A1 EP 1753884A1 EP 05745341 A EP05745341 A EP 05745341A EP 05745341 A EP05745341 A EP 05745341A EP 1753884 A1 EP1753884 A1 EP 1753884A1
Authority
EP
European Patent Office
Prior art keywords
agglomerate
fine
stones
solidification
iron ore
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Withdrawn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
EP05745341A
Other languages
German (de)
English (en)
Inventor
Horst MITTELSTÄDT
Stefan WIENSTRÖER
Reinhard Fusenig
Ronald Erdmann
Klaus Kesseler
Matthias Rohmann
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.)
ThyssenKrupp Steel Europe AG
Original Assignee
ThyssenKrupp Steel 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 ThyssenKrupp Steel AG filed Critical ThyssenKrupp Steel AG
Publication of EP1753884A1 publication Critical patent/EP1753884A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/14—Agglomerating; Briquetting; Binding; Granulating
    • C22B1/24—Binding; Briquetting ; Granulating
    • C22B1/242—Binding; Briquetting ; Granulating with binders
    • C22B1/243—Binding; Briquetting ; Granulating with binders inorganic
    • 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
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/02—Working-up flue dust
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D1/00—Casings; Linings; Walls; Roofs
    • F27D1/0003—Linings or walls
    • F27D1/0006—Linings or walls formed from bricks or layers with a particular composition or specific characteristics
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D1/00—Casings; Linings; Walls; Roofs
    • F27D1/04—Casings; Linings; Walls; Roofs characterised by the form, e.g. shape of the bricks or blocks used
    • 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
    • C22B1/00—Preliminary treatment of ores or scrap
    • 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
    • Y02P10/20—Recycling

Definitions

  • the invention relates to an agglomerate stone for use in shaft, Corex or blast furnaces, a method for producing such agglomerate stones and the use of fine or very fine iron ore dusts.
  • iron-containing dusts with the finest and fine grain of up to 3 mm are obtained in large quantities. In order to be able to use these dusts for metal production, they have to be cut into pieces. Sintering and pelleting are common processes for making fine and fine ores used in smelting.
  • sintering ore dust When sintering ore dust, a mixture of moistened fine ore together with coke breeze or another carbon carrier and aggregates of limestone, quicklime, olivine or dolomite is usually placed on a circumferential grate, the so-called “sintering belt” and ignited from above. The carbon contained in this mixture burns with the help of the air drawn through the sintering belt, causing the ore grains to cake. When the end of the sintering belt is reached in this way the layer on the belt is completely sintered. The solidified iron ore is broken, sieved while still glowing and fed to a cooler, in which it is cooled so gently that its strength is not impaired. The sinter obtained after further screening of the fine components of the cooled sinter mixture is suitable for direct use in the blast furnace due to its high gas permeability and good reducibility.
  • the known sintering process can usually only economically bring ore dusts into a lumpy form that have grain sizes of 2 mm and more. Ore dust with a significantly lower grain size can be used for metal extraction by pelleting.
  • pellets produced by pelleting can have a uniform grain compared to lump ores, a constant one Quality and good gas flow during the reduction can be guaranteed.
  • pellets can therefore only be used to a limited extent.
  • the blocks are then heated to a temperature above 1000 ° C when they sink from the high filling position towards the hot zone of the OxiCup furnace.
  • the carbon carrier contained in the blocks is converted into CO gas, which causes a direct reduction in the iron oxide content of the blocks.
  • the OxiCup process thus provides an economical method for reusing dusts from iron production.
  • the invention proposes an agglomerate stone for use in shaft, Corex or blast furnaces, which (in% by weight) 6 - 15% of a cement binder, up to 20% of a carbon carrier, up to 20% of residual and recyclable materials, optionally up to 10% of a solidification and solidification accelerator, and the remainder of the iron ore present in stone format in the form of particles with a grain size of less than 3 mm and an early strength of at least after three days 5 N / mm 2 and after 28 days has a cold compressive strength of at least 20 N / mm 2 .
  • iron ore fine and very fine dusts which are in stone format are used in accordance with the invention.
  • Such iron ores contain essentially no metallic iron, but only pure iron oxide, which can be contaminated with little gait. Therefore, agglomerate stones according to the invention have fundamentally different properties than those in. State of the art so far from residual and circular waste stones.
  • Ore stones of the type according to the invention have a significantly higher early and final strength than the known residual material stones. Due to the high compressive strength of at least 20 N / mm 2 present in the finished state in the case of agglomerate stones according to the invention, they can safely withstand the pressure of the pouring column in the blast furnace.
  • agglomerate stones according to the invention regularly achieve a minimum hot compressive strength of 10 N / mm 2 .
  • composition of the ore stones according to the invention is coordinated with one another in such a way that in blast furnace use, when the binding properties of the cement material collapse with increasing temperature and heating duration, the latter Temperature-forming sponge iron as a supporting structure, the gas permeability of the stone and of the entire furnace content can be maintained.
  • the particular strength and shape retention of agglomerate stones according to the invention make these stones particularly suitable for use in shaft, Corex or blast furnaces.
  • agglomerate stones according to the invention can contain up to 20% of residual and circular substances also contributes to the advantages of the invention with regard to the problem of disposal of residual and circular substances.
  • residual and circular substances are mixtures of materials which, in addition to iron in metallic and oxidic form Contain impurities.
  • Such residual and recycle materials occur, for example, in the production and processing of steel in the form of filter dusts, top dusts or mill scale.
  • the final strength of the agglomerate stones according to the invention is in each case so high that they withstand the loads which occur when used in the respective furnace. Since agglomerate stones according to the invention can be significantly larger, they are suitable for use in large furnaces, such as shaft, Corex or blast furnaces, and there ensure the improved gasification during the reduction.
  • the early strength of the agglomerate stones obtained according to the invention is sufficient for them to be able to be transported a short time after their manufacture. This makes it possible, for example, to stack the agglomerate stones according to the invention soon after they have been formed in a drying room, in which they can then be dried particularly effectively.
  • Agglomerate stones according to the invention can be produced on stone-making machines known per se, such as are used for example for the production of paving stones.
  • Such block making machines allow a particularly cost-effective production and contribute to the fact that agglomerated stones according to the invention can be produced at a particularly favorable • the economics of their use further enhancing price.
  • agglomerate stones according to the invention enable the economical use of iron ore dusts over the entire width of the conceivable grain sizes up to 3 mm.
  • dusts with a grain size of up to 1 mm can be processed and used just as easily as iron ore dust with a grain size of up to 500 ⁇ m that typically occurs in the area of certain deposits.
  • Such ore dust which is obtained in the range from 5 to 30 ⁇ m when pelleting iron ores, so-called "pellet feed”, can also be used in that agglomerate stones according to the invention are produced from them.
  • Studies show that even dusts collected in aqueous solution and produced in the production of ore concentrates with grain sizes of up to 7 ⁇ m can be used profitably for iron production if they are used to form agglomerate stones according to the invention.
  • the iron ores contained in fine-grained agglomerate stones according to the invention are preferably in haematitic (Fe 2 0 3 ), magnetitic (Fe 3 0 4 ) and / or wustitic (FeO) modification, the grain diameter of which is also preferably less than 0.1 mm.
  • the invention also makes it difficult to sinter or pelletize to supply ferrous materials for the production of pig iron. Accordingly, iron ore in the form of geothite (FeO (OH)) can be used for the production of agglomerate stones according to the invention. This applies even if the geothite has a grain size of up to 2 mm, whereby grain sizes that are significantly smaller than 2 mm can also be used.
  • FeO geothite
  • the content of iron should be at least 40% by weight in an agglomerate stone according to the invention.
  • the invention makes use of the idea, already known per se, of coldly binding the iron dust to be used in stone form without special heat treatment with the aid of a cement.
  • cement binding also enables slag guidance, in particular its proportions of MgO, CaO, SiO 2 , Al 2 O 3 , during the production of pig iron, via the respective cement portion of the agglomerate stone. to vary.
  • Portland cement or metallurgical cement which is available at low cost, can be used as the cement binder.
  • the binder in question is mixed with the iron ore dust as a hydraulic cement phase.
  • the early strength determined after 3 days becomes at least 5 N / mm 2 and that which can be determined after 28 days
  • Cold compressive strength of at least 20 N / mm 2 achieved in each case particularly reliably with agglomerate stones according to the invention.
  • the special behavior of the agglomerate stones according to the invention when heated has turned out to be particularly advantageous for use in a furnace for producing pig iron.
  • the embedding of the iron ore dust present in stone format in a cement binder at temperatures of up to 400 ° C. results in an increase in strength.
  • the temperature range of more than 400 ° C to 800 ° C there is only a slow decrease in strength. Due to this behavior, the agglomerate stones keep their shape as long as they pass through the furnace, so that they are safely transported to the hot melting zone. Only at temperatures above 800 ° C to 1000 ° C does their strength drop faster.
  • the iron sponge formed in this temperature range during the reduction ensures the shape retention of the agglomerate stone during further heating and maintains its gas permeability.
  • the agglomerate stone according to the invention can, in addition to the cement binder, optionally also a setting and solidification accelerator, such as water glass, alumina cement, calcium chloride, an alkali salt, in particular a Na salt, or a Cellulose glue, such as paste, included.
  • a setting and solidification accelerator such as water glass, alumina cement, calcium chloride, an alkali salt, in particular a Na salt, or a Cellulose glue, such as paste, included.
  • the ore stones processed according to the invention in dust form can be used both directly-reducing with a reducing agent (carbon carrier) and without a reducing agent. If a reducing agent is present, the maximum content of the carbon carrier in the agglomerate stone should not be more than 20% by weight.
  • an optimal adaptation of the proportion to the proportion by weight of iron is achieved if the agglomerate stone contains 8-15% by weight of the carbon carrier.
  • the proportion of volatile components in an agglomerate stone according to the invention is high, the otherwise reduced reducibility can be compensated for by increased contents of the C-carrier component.
  • the grain size of the carbon carrier is preferably up to 2 mm. C-beams with such a grain size are available at particularly low cost and are difficult to use when extracting iron.
  • Agglomerate stones according to the invention should have a cylindrical, cuboid or polygonal shape, on the one hand to ensure sufficient stability and on the other hand after filling into the furnace to ensure that there are sufficient gaps between them for the through-gasing of the bed.
  • the shaping surface is optimally used.
  • the water content of the agglomerate stone according to the invention should be less than 25%. The production of earth-moist, crumbly green bodies is simplified compared to the processing of masses with a higher moisture content. In addition, by limiting the water content of the green bodies according to the invention, it is avoided that excess water in the oven has to be expelled with high energy expenditure.
  • Agglomerate stones according to the invention are particularly easy to produce.
  • stone-like iron ore in the form of fine or very fine dust with a maximum grain size of 3 mm with a binder present as a hydraulic cement phase as well as optionally with a carbon carrier, with residual and circulating materials and / or a solidification and solidification accelerator with the stipulations mixed that the proportion of cement binder in the mixture obtained (in wt .-%) 6 - 15%, the proportion of the carbon carrier up to 20%, the proportion of residual and circulating materials up to 20% and the proportion of solidification and solidification accelerators up to 10%.
  • the mixture obtained is filled into molds. According to a first process variant, the mixture is then pressed before it is dried.
  • Diag. 1 the strength of an agglomerate stone according to the invention plotted against the temperature
  • Diag. 2 the strength of a conventional agglomerate stone plotted against temperature
  • Diag. 3a the temperature of an agglomerate stone according to the invention plotted over the heating time
  • Diag. 3b the stone height of an agglomerate stone according to the invention plotted over the heating-up time
  • Diag. 3c shows the weight loss of an agglomerate stone according to the invention plotted over the heating-up time.
  • the agglomerate stones examined were each subjected to the so-called "modified RuL test".
  • the melting behavior of the agglomerate stones in the chimney shaft is simulated with a chimney gas atmosphere under static conditions. In this way, statements can be made as to whether the formation of sponge iron from the reduction of the iron carriers of the agglomerate stones is sufficient to counteract the breakdown of the cement bond that occurs with increasing warming, without the gasification of the chimney being negatively affected by softening or disintegration of the agglomerate stones is hindered.
  • the simulation ends in the temperature range of 1000 - 1100 ° C.
  • the grain size of the iron ore dust was between 5 and 30 ⁇ m.
  • the iron ore dust was mixed with coke in the form of coke dust as a carbon carrier and a quick-setting, commercially available standard cement as a cement binder.
  • the mixture obtained contained (in% by weight) 70 to 80% iron dust, 10 to 15% coke and 10 to 15% cement binder.
  • the mixture composed in this way was shaken in a known stone molding machine and pressed to block-shaped agglomerate stones, which had a hexagonal base with an edge length of approx. 30 mm and a height of 110 mm. After drying, the agglomerate stones were subjected to the RuL test. This resulted in a degree of reduction
  • Diag. 3b is the weight loss dG, which occurs in g as the heating time t h increases , of the agglomerate stones (line “KS”) produced using coal dust and tested in experiment I (line “KS”) and that produced using charcoal as a carbon carrier, but otherwise with those in the experiment I matching agglomerate stones (line “HK”) again applied over the heating time t h .
  • KS agglomerate stones
  • HK agglomerate stones
  • the diagrams 3a - 3c show by the observed change in the increase in the stone temperature T s , the height H s and the weight loss dG of the agglomerate stones KS and HK, that metallization begins at temperatures above 800 ° C.
  • This process can be observed independently with both investigated carbon carrier materials (coke dust, charcoal).
  • the support structure that forms as a result of the metallization counteracts the drop in strength that occurs at high temperatures, so that up to the area of a blast furnace where the solid material becomes plastic on its way down due to the ever higher temperatures (“cohesive zone”) sufficient strength of the agglomerate stones is guaranteed for the gasification and locomotion.
  • iron ore dust is initially from a concentrate that came from the Carol Lake, Canada deposit, with a grain size of up to 500 ⁇ m and a hematite / magnetite ratio of 1: 1 with coke dust as a carbon carrier and a quick-setting one , standard commercial cement has been mixed as a cement binder.
  • the mixture obtained contained (in% by weight) 70 to 80% iron ore dust, 10 to 15% coke dust and 10 to 15% cement.
  • Agglomerate stones were produced from the mixture composed in this way in the manner already explained for experiment I.
  • the agglomerate stones obtained in this way were also subjected to the modified RuL test.
  • the degree of reduction was 95.6% and the degree of decarburization was 85%.
  • the trivalent iron level was completely reduced.
  • iron dust consisting of magnetite and a grain size of up to 1 mm from a concentrate, which came from the Guelbs / Kedia deposit, Mauritania, was also mixed with coke dust and quick-setting, commercially available cement binder.
  • the iron ore content of the mixture obtained was 75% by weight, its coke content 13% by weight and its cement content 12% by weight.
  • the agglomerate stones also produced from this mixture in the manner already described in connection with experiment 1 have also been subjected to the RuL test. It gave a degree of reduction of 88.3% and a degree of decarburization of 83.2%.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Environmental & Geological Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

L'invention concerne une pierre agglomérée qui permet d'utiliser de manière économique les poussières de minerai résultant de l'extraction et de la préparation du minerai de fer, ces poussières n'étant pas mises en valeur jusqu'à présent. La pierre agglomérée de l'invention contient, en pourcentages en poids, 6 - 15 % d'un liant de ciment, jusqu'à 20 % d'un support de carbone, jusqu'à 20 % de substances résiduelles et de matières de recyclage, éventuellement jusqu'à 10 % d'un accélérateur de prise et de durcissement, le reste en format de pierre étant du minerai de fer en forme de particules de granulométrie inférieure à 3 mm. La pierre agglomérée présente une résistance initiale d'au moins 5 N/mm2 au bout de trois jours et une résistance à froid sous charge d'au moins 20 N/mm2 au bout de 28 jours. De résistance (St) et de tenue de forme élevées, même à hautes températures T, cette pierre agglomérée est particulièrement adaptée à l'utilisation dans des fours à cuve, des fours Corex et hauts fourneaux. La présente invention porte également sur un procédé pour réaliser ladite pierre agglomérée.
EP05745341A 2004-06-03 2005-05-25 Pierre agglomeree pour fours a cuve, fours corex et hauts fourneaux, procede pour fabriquer cette pierre agglomeree et utilisation de poussieres de minerai de fer fines et hyperfines Withdrawn EP1753884A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE200410027193 DE102004027193A1 (de) 2004-06-03 2004-06-03 Agglomeratstein zum Einsatz in Schacht-, Corex- oder Hochöfen, Verfahren zur Herstellung von Agglomeratsteinen und Verwendung von Eisenerz-Fein- und -Feinststäuben
PCT/EP2005/005626 WO2005118892A1 (fr) 2004-06-03 2005-05-25 Pierre agglomeree pour fours a cuve, fours corex et hauts fourneaux, procede pour fabriquer cette pierre agglomeree et utilisation de poussieres de minerai de fer fines et hyperfines

Publications (1)

Publication Number Publication Date
EP1753884A1 true EP1753884A1 (fr) 2007-02-21

Family

ID=34968601

Family Applications (1)

Application Number Title Priority Date Filing Date
EP05745341A Withdrawn EP1753884A1 (fr) 2004-06-03 2005-05-25 Pierre agglomeree pour fours a cuve, fours corex et hauts fourneaux, procede pour fabriquer cette pierre agglomeree et utilisation de poussieres de minerai de fer fines et hyperfines

Country Status (10)

Country Link
US (1) US8025727B2 (fr)
EP (1) EP1753884A1 (fr)
CN (1) CN1961085A (fr)
AU (1) AU2005250105B2 (fr)
BR (1) BRPI0511806A (fr)
CA (1) CA2569247A1 (fr)
DE (1) DE102004027193A1 (fr)
RU (1) RU2366735C2 (fr)
UA (1) UA87686C2 (fr)
WO (1) WO2005118892A1 (fr)

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DE102005062036A1 (de) * 2005-12-22 2007-06-28 Thyssenkrupp Steel Ag Agglomeratstein zum Einsatz in Schacht-, Corex- oder Hochöfen
DE102007058125B4 (de) * 2007-11-30 2013-11-28 Chemische Fabrik Budenheim Kg Metallrückstände und Kohlenstoffträger enthaltender Formkörper
UA107947C2 (ru) 2009-11-17 2015-03-10 Вале С.А. Агломерат мелкой руды, который используется в процессе агломерации, и способ получения агломерата рудной мелочи
DE102010031101A1 (de) 2010-07-08 2012-01-12 Mfg Metall- Und Ferrolegierungsgesellschaft Mbh Hafner, Blondin & Tidou Verfahren zur Herstellung von Legierungsformlingen
JP2013209748A (ja) * 2012-02-28 2013-10-10 Kobe Steel Ltd 還元鉄塊成物の製造方法
EP2662457A1 (fr) * 2012-05-07 2013-11-13 Siemens VAI Metals Technologies GmbH Procédé et dispositif pour la fabrication d'agglomérés et l'utilisation les agglomérés d'un procédé FINEX ®
BR102019023195B1 (pt) * 2019-11-05 2021-01-19 Vale S.A. processo de produção de aglomerado de finos de minério de ferroe o produto aglomerado
EP4342865A1 (fr) 2022-09-22 2024-03-27 ThyssenKrupp Steel Europe AG Brique agglomérée destinée à être utilisée dans un four électrique

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Also Published As

Publication number Publication date
RU2006146980A (ru) 2008-07-20
BRPI0511806A (pt) 2008-01-15
AU2005250105A1 (en) 2005-12-15
CA2569247A1 (fr) 2005-12-15
AU2005250105B2 (en) 2010-07-22
DE102004027193A1 (de) 2005-12-29
US8025727B2 (en) 2011-09-27
US20080250980A1 (en) 2008-10-16
RU2366735C2 (ru) 2009-09-10
WO2005118892A1 (fr) 2005-12-15
UA87686C2 (ru) 2009-08-10
CN1961085A (zh) 2007-05-09

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