EP2937427B1 - Reduced-iron production method - Google Patents

Reduced-iron production method Download PDF

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Publication number
EP2937427B1
EP2937427B1 EP12890530.4A EP12890530A EP2937427B1 EP 2937427 B1 EP2937427 B1 EP 2937427B1 EP 12890530 A EP12890530 A EP 12890530A EP 2937427 B1 EP2937427 B1 EP 2937427B1
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EP
European Patent Office
Prior art keywords
iron
ore
zinc
mixture
alkali
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EP12890530.4A
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German (de)
English (en)
French (fr)
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EP2937427A1 (en
EP2937427A4 (en
Inventor
Sang Han Son
Byung Kook Cho
Hae Kwon Jeong
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Posco Holdings Inc
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Posco Co Ltd
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Publication of EP2937427A4 publication Critical patent/EP2937427A4/en
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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
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/14—Agglomerating; Briquetting; Binding; Granulating
    • C22B1/24—Binding; Briquetting ; Granulating
    • 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
    • C22B1/16—Sintering; Agglomerating
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B13/00—Making spongy iron or liquid steel, by direct processes
    • C21B13/006—Starting from ores containing non ferrous metallic oxides
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B13/00—Making spongy iron or liquid steel, by direct processes
    • C21B13/10—Making spongy iron or liquid steel, by direct processes in hearth-type furnaces
    • 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
    • C22B1/244—Binding; Briquetting ; Granulating with binders organic
    • C22B1/245—Binding; Briquetting ; Granulating with binders organic with carbonaceous material for the production of coked agglomerates
    • 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
    • C22B19/00—Obtaining zinc or zinc oxide
    • 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
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • 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
    • C22B4/00—Electrothermal treatment of ores or metallurgical products for obtaining metals or alloys
    • C22B4/08—Apparatus
    • 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

Definitions

  • the present invention relates to a method for producing reduced iron. More particularly, the present invention relates to a method for producing high reduced rate iron from iron ore abundant in phosphorous, zinc and alkali element impurities, with the concomitant recovery of phosphorous, zinc and alkali elements.
  • reduced iron is used as a material for making molten iron or molten steel.
  • Reduced iron is produced from reduction of an oxidized iron source, such as iron ore or oxidized iron by a carbonaceous reducing agent (hereinafter referred to as "carbonaceous material") or a reducing gas. This process, called direct reduction, is most commonly used to produce reduced iron.
  • carbonaceous material carbonaceous reducing agent
  • direct reduction is most commonly used to produce reduced iron.
  • a rotary hearth furnace For producing direct reduced iron (DRI), a rotary hearth furnace (RHF) is utilized in which pellets composed of extremely trace iron ore are reduced.
  • RHF rotary hearth furnace
  • Patent Documents 1 and 2 are directed to the production of reduced iron using a rotary furnace.
  • particle sizes of raw materials are controlled to improve reactivity, thereby producing a reduced iron pellet in which a metallization ratio is increased while Patent Document 2 discloses the production of iron ore rich in zinc.
  • conventional rotary furnaces are compactly configured to reduce iron ore at up to 1,350°C in a reducing atmosphere, it is difficult to maintain the reducing atmosphere within such furnaces.
  • conventional rotary furnaces are not suitable for use in mass scale production due to their annual capacity of production amounting only to 150,000 ⁇ 500,000 tons.
  • the reduced iron may be re-oxidized by the oxidative atmosphere, which is also a cause of poor reduction rate.
  • phosphorus (P), zinc (Zn) and alkali oxides (K 2 O+Na 2 O) within iron ore are impurities that may cause various defects in the final reduced iron product.
  • Iron ore that has a lower content of phosphorus (P), zinc (Zn), and alkali oxides (K 2 O+Na 2 O) is preferred.
  • the present invention provides a method for producing reduced iron under an oxidative atmosphere in an open-type furnace.
  • a mixture of iron ore and carbonaceous material is molded into ore agglomerates and sufficiently reduced under an oxidative atmosphere in a reducing furnace.
  • the present invention provides a method for producing reduced iron by which a broad spectrum of iron ores including iron ores rich in one or more of phosphorus (P), zinc (Zn), or alkali oxide (K 2 O+Na 2 O can be used to effectively produce reduced iron.
  • the present invention provides a method for producing reduced iron by which phosphorus (P), zinc (Zn) and alkali oxides (K 2 O+Na 2 O) can be separated and recovered from the iron ores.
  • the present invention provides a method for producing reduced iron, comprising: mixing an iron material bearing phosphorus, zinc and alkali oxides with a carbonaceous material to prepare a mixture, wherein the mixture has a basicity (CaO/SiO 2 ) of 1 or greater; forming the mixture into ore agglomerates; reducing the ore agglomerates in an open-type reducing furnace, with concomitant removal of phosphorus, zinc and alkali elements from the ore agglomerates; crushing the reduced ore agglomerates to separate reduced iron from phosphorus-bearing slag; and agglomerating the reduced iron while recovering the slag, wherein the carbonaceous material is used in an amount of 10 parts by weight or greater, based on 100 parts by weight of the mixture, wherein the open-type reducing furnace is heated to a temperature of 1,000°C or higher.
  • the mixture contains phosphorus (P) in an amount of 0.06 % by weight or greater, zinc (Zn) in an amount of 0.02 % by weight or greater, and an alkali oxide (K 2 O+Na 2 O) in an amount of 0.1 % by weight or greater.
  • the iron material is selected from among an iron ore having a phosphorus (P) content of 0.06 % or greater, an iron ore having a zinc (Zn) content of 0.02 % or greater, an iron ore having an alkali oxide (K 2 O+Na 2 O) content of 0.1 % or greater, and a combination thereof.
  • the carbonaceous material contains carbon-bearing dust generated from a coal mining site or a steelworks or both.
  • the mixture has an alkali oxide content of 0.5 % or greater.
  • the mixture is further supplemented with a subsidiary material for adjusting basicity and an alkali oxide content, said subsidiary material including CaO to adjust the basicity of the mixture, and Na 2 CO 3 and K 2 CO 3 to adjust the alkali oxide content of the mixture.
  • the reducing furnace maintains an oxidative atmosphere therein during the reducing step in which gas is generated upon the reduction of the carbonaceous material within the ore agglomerates, forming a gas film that surrounds the ore agglomerates and thus blocks the ore agglomerates from the oxidative atmosphere.
  • the open-type reducing furnace is heated to a temperature of 1,000°C or higher to calcine the ore agglomerates, and operated for a limited period of time at maximum such that carbon is completely depleted of the ore agglomerates.
  • the reducing step comprises recovering the zinc within the ore agglomerates as a dust in an exhaust gas from the open-type furnace, water granulating the recovered dust to separate zinc oxide (ZnO), and recovering the zinc oxide.
  • zinc within the ore agglomerates is vaporized during the reduction step in the reducing furnace, discharged together with the exhaust gas, and reacted with oxygen of the exhaust gas to form zinc oxide (ZnO), said zinc oxide being recovered as a dust.
  • the recovered dust is water granulated during which the alkali element is separated and recovered together with the water.
  • the reduced iron is separated from the slag using a magnetic seperator.
  • the present invention provides a method for producing reduced iron, comprising: mixing an iron material with a carbonaceous material to form ore agglomerates, and reducing the ore agglomerates in an open-type furnace.
  • the carbonaceous material is used in an amount of 10 parts by weight or greater, based on 100 parts by weight of the ore agglomerates, and wherein the reducing furnace maintains an oxidative atmosphere therein during the reducing step in which gas is generated upon the reduction of the carbonaceous material within the ore agglomerates, thus forming a gas film that surrounds the ore agglomerates and blocks the ore agglomerates from the oxidative atmosphere.
  • the present application discloses an apparatus of producing reduced iron, comprising: a plurality of raw material hoppers for respectively storing different types of iron ores therein; a carbonaceous material hopper for storing a carbonaceous material therein; a mixer for mixing the effluent of different types of iron ores from the raw material hoppers with the carbonaceous material from the carbonaceous material hopper; a first molding press for forming the mixture into ore agglomerates; an open-type reducing furnace for reducing the ore agglomerates in an oxidative atmosphere; a spaller for crushing the ore agglomerates reduced in the reducing furnace; a magnetic separator for separating the crushed, reduced particles into reduced iron and slag by magnetism; and a second molding press for molding the reduced iron
  • the apparatus may further comprise: a collector for collecting dust from an exhaust gas from the reducing furnace; and a water granulator for granulating the collected dust with water to separate zinc oxide from alkali element-bearing waste water.
  • iron ores avoided for use in conventional iron making processes due to their high impurity content can be employed for producing reduced iron on a mass scale under an oxidative atmosphere using an open-type furnace in accordance with the present invention.
  • the method of the present invention is provided for producing reduced iron, comprising: mixing an iron material with a carbonaceous material to form ore agglomerates; and reducing the ore agglomerates in an open-type furnace, wherein the reducing furnace maintains an oxidative atmosphere therein during the reducing step in which gas is generated upon the reduction of the carbonaceous material within the ore agglomerates, thus forming a gas film that surrounds the ore agglomerates and blocks the ore agglomerates from the oxidative atmosphere.
  • impurities such as phosphorus (P), zinc (Zn), and alkali oxides (K 2 O+Na 2 O) contained in iron ores can be utilized in the reducing step, and can be recovered from the iron.
  • FIG. 1 there is a schematic view illustrating an apparatus and method for producing reduced iron.
  • the apparatus of producing reduced iron comprises a first spaller 11 for crushing iron ore; a plurality of hoppers 21, 22 and 23 for storing the iron ore crushed in the first spaller 11 by type therein; a second spaller 12 for crushing a carbonaceous material, such as coal; a carbonaceous material hopper 30 for storing the carbonaceous material crushed by the second spaller 12 therein; a mixer 50 for mixing effluent from different types of iron ore from the raw material hoppers 21, 22 and 23 with the crushed carbonaceous material from the carbonaceous material hopper 30; a first molding press 61 for forming the mixture into ore agglomerates; an open-type reducing furnace 70 for reducing the ore agglomerates in an oxidative atmosphere; a third spaller 13 for crushing the ore agglomerates reduced in the reducing furnace 70; a magnetic separator 80 for separating the crushed, reduced particles into reduced iron and slag by magnetis
  • the apparatus may further comprise at least one subsidiary material hopper 40 for storing a subsidiary material therein; a collector 90 for collecting dust from an exhaust gas from the reducing furnace; and a water granulator 100 for granulating the collected dust with water to separate zinc oxide from alkali element-bearing waste water.
  • the open-type reducing furnace has an internal space that is open rather than closed. So long as it can heat ore agglomerates while continuously transporting the ore agglomerates, any reducing furnace, without limitations to specific configurations, may be employed.
  • an open-type reducing furnace may be provided with a transport means for transporting ore agglomerates in a conveyer manner.
  • a furnace body defining an internal space in which the ore agglomerates are conveyed and reduced is located above the transport means.
  • the internal space of the furnace body is heated by a plurality of burners installed therein.
  • a suction means for aspirating air from the internal space of the furnace body is provided below the transport means.
  • ore agglomerates are conveyed by the transport means while heat flows downwardly from an upper space of the ore agglomerates by the combustion of the burners and the aspiration of the suction means.
  • ore agglomerates can be arranged in a multi-layer pattern and can be continuously reduced to produce reduced iron on a mass scale.
  • Each of the first molding press 61 and the second molding press 62 is a twin role structure.
  • the iron ores are crushed in the first spaller 11 shown in FIG. 1 and individually stored in the iron raw hoppers 21, 22 and 23 by type.
  • the iron ores may have a phosphorus (P) content of 0.06 % or greater, a zinc (Zn) content of 0.02 % or greater, an alkali oxide (K 2 O+Na 2 O) content of 0.1 % or greater, or a combination thereof.
  • a carbonaceous material is crushed in the second spaller 12 and stored in the carbonaceous material hopper 30.
  • the carbonaceous material may contain carbon-bearing dust generated from a coal mining site or a steelworks or both.
  • the carbonaceous material preferably has a particle size of 0.1 mm or less so as to enhance reactivity.
  • the subsidiary material hopper 40 stores a subsidiary material for adjusting basicity and a subsidiary material for adjusting the content of alkali oxides, in combination or separately, therein.
  • CaO may be used as a subsidiary material for adjusting basicity, and the content of alkali oxides may be adjusted with Na 2 CO 3 or K 2 CO 3 or both.
  • the iron ore, the carbonaceous material, and the subsidiary materials are each weighed, introduced into the mixer 50, and mixed to give a mixture.
  • the mixture comprises phosphorus (P) in an amount of 0.06 % or greater, zinc (Zn) in an amount of 0.02 % or greater, and an alkali oxide (K 2 O+Na 2 O) in an amount of 0.1 % or greater, which are mostly derived from the iron ore and the carbonaceous material.
  • P phosphorus
  • Zn zinc
  • K 2 O+Na 2 O alkali oxide
  • the ore agglomerates are preferably maintained to have a high basicity and a high alkali oxide content in order to sufficiently isolate phosphorus during the reduction of ore agglomerates.
  • CaO, Na 2 CO 3 , and K 2 CO 3 are preferably added in such amounts as to adjust the basisicity (CaO/SiO 2 ) of the mixture to 1 or higher and to maintain an alkali oxide content of 0.5 % in the mixture.
  • the reason why the basicity and the alkali oxide content are limited will be revealed later in the description given in conjunction with FIGS. 2 and 3 .
  • the mixture thus obtained is fed to the first molding press 61 where homogeneously sized ore agglomerates are formed.
  • the ore agglomerates are introduced into the open-type reducing furnace 70 where iron (Fe) of the ore agglomerates is reduced in an oxidative atmosphere while separating phosphorus, zinc and alkali elements from the iron.
  • the oxidative atmosphere means exposure to air without any atmospheric control.
  • Iron oxides within the ore agglomerates react (are reduced), as shown in the following Chemical Formula 1, to generate Fe and CO. Then, this CO reacts with (reduces) the iron oxides of the ore agglomerates as shown in the following Chemical Formula 2, with the concomitant generation of iron (Fe) and CO 2 .
  • This CO 2 may be converted into CO by reaction with carbon within the ore agglomerates.
  • the CO and CO 2 gases that are generated by reactions between iron oxides and carbon within the ore agglomerates are exhausted externally, forming a gas film surrounding the ore agglomerates. As the gas film serves to block the ore agglomerates from the oxidative atmosphere of the open-type reducing furnace 70, the reduction of the ore agglomerates can be facilitated in the open-type reducing furnace 70.
  • a sufficient amount of the gas film is formed by fully reacting iron oxides of the ore agglomerates with carbon.
  • a sufficient amount of carbon is contained in the ore agglomerates.
  • the carbonaceous material is mixed in an amount of 10 parts by weight or greater, based on 100 parts by weight of the total mixture.
  • the open-type reducing furnace 70 is maintained to have a calcination temperature of 1,000oC or higher to reduce the ore agglomerates.
  • FIG. 4 is a graph showing the metallization ratio of ore agglomerates versus the temperature of the open-type reducing furnace according to the amount of the carbonaceous material. As can be seen, ore agglomerates containing a carbonaceous material in an amount of 10 parts by weight were found to allow sufficient metallization.
  • the time of the reduction of the ore agglomerates is preferably limited at maximum to an extent that carbon is completely depleted of the ore agglomerates.
  • the ore agglomerates undergo a reaction to form a slag containing the elements in the form of, for example, CaO ⁇ (P 2 O 5 ).
  • the ore agglomerates are in the mixture of reduced iron and slag.
  • zinc oxide and alkali oxides are reduced at lower temperatures than are iron oxides, and are discharged as an exhaust gas.
  • the zinc (Zn) vaporized during the reduction of the ore agglomerates reacts with oxygen in the exhaust gas to form a zinc oxide (ZnO) that is then collected as a dust by the collector 90.
  • the alkali elements are also vaporized, exhausted as a gas, and reacted with oxygen of the exhaust gas to form an alkali oxide. Likewise, this oxide is collected as a dust by the collector 90.
  • waste water containing crude zinc oxide and alkali elements is recovered.
  • the ore agglomerates in mixture with reduced iron and slag are crushed in the third spaller 13 and separated into reduced iron and slag by magnetism in the magnetic separator 80.
  • the reduced iron thus obtained is formed into briquettes of a predetermined size in the second molding press 62 while the slag rich in CaO and phosphorus may be recycled as a fertilizer material.
  • Iron ores rich in phosphorus, zinc and alkali elements (Na 2 O, K 2 O) were used. Each iron ore was formed into briquettes rich in phosphorus, zinc and alkali elements.
  • zinc oxide, phosphorus oxide and alkali oxides all in a reagent grade, were added to maximize contents of zinc, phosphorus and alkali elements.
  • iron ore C the composition of an iron ore that is used in a typical iron making process
  • iron ore C which is used in a typical iron making process
  • Iron ores A and B were independently mixed with coal (20 % by weight) and formed into briquettes.
  • CaO, K 2 O, and Na 2 O in a reagent grade were added. Under a reducing furnace simulated condition, the briquettes were reduced.
  • a reduction experiment was carried out on the briquettes by elevating the temperature at a rate of 50oC/min to a reduction temperature of 1,200oC and by maintaining the reduction temperature for 20 min. Then, the briquettes were analyzed for Fe, Zn, and P content while Fe, Zn, P, K, and Na content in the slag is examined.
  • FIG. 2 is a graph illustrating phosphorus recovery rates in slag versus basicity after the reduction of ore agglomerates at 1,200oC for 20 min
  • FIG. 3 is a graph illustrating phosphorus recovery rates of slag versus alkali oxide content in ore agglomerates after the reduction of ore agglomerates having a basicity of 1 at 1200oC for 20 min.
  • the phosphorous recovery rate in slag gradually increases with an increase in basicity.
  • the phosphorus oxide P 2 O 5
  • its stability is maintained in the condition of high basicity.
  • phosphorus oxide in the slag is stable even when a strong alkali such as alkali oxide is added. Therefore, the addition of small amounts of highly basic slag and alkali oxide is effective in preventing phosphorus oxide from being reduced and dissolved into the metal Fe during the reduction of reduced iron, and thus in allowing phosphorus oxide to exist in the slag.
  • the briquettes were found to have a reduction rate of approximately 85 ⁇ 90% irrespective of basicity.
  • the zinc content in the slag after reduction was decreased to approximately 0.004 % from 0.1 % in the initial phase.
  • Reduction of zinc oxide to metal Zn occurred at a lower temperature than reduction of iron oxide to its metal. Soon after reduction into metal zinc, it was vaporized, exhibiting a high vapor pressure. The gaseous zinc was re-oxidized into and discharged as ZnO in exhaust gas.
  • the recovery rate of phosphorous in slag was observed to increase with an increase in the alkali oxide content of the briquettes.
  • the use of alkali oxide-rich iron ore in mixture with phosphorus-rich iron ore is advantageous in enhancing phosphorus recovery rates in slag. Accordingly, it was found that phosphorus could be recovered to a desired degree when the mixture was set to have a basicity (CaO/SiO 2 ) of 1 or higher, and an alkali oxide content of 0.5 % or higher.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
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  • Manufacture And Refinement Of Metals (AREA)
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EP12890530.4A 2012-12-18 2012-12-27 Reduced-iron production method Active EP2937427B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020120148940A KR101442920B1 (ko) 2012-12-18 2012-12-18 환원철 제조방법 및 제조장치
PCT/KR2012/011650 WO2014098300A1 (ko) 2012-12-18 2012-12-27 환원철 제조방법 및 제조장치

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EP2937427A1 EP2937427A1 (en) 2015-10-28
EP2937427A4 EP2937427A4 (en) 2017-03-01
EP2937427B1 true EP2937427B1 (en) 2020-08-05

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KR (1) KR101442920B1 (zh)
CN (1) CN104870660A (zh)
AU (1) AU2012397402B2 (zh)
BR (1) BR112015014606B1 (zh)
WO (1) WO2014098300A1 (zh)

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KR101626602B1 (ko) * 2014-12-05 2016-06-01 주식회사 포스코 분환원철 괴성화 방법, 분환원철 괴성화 장치 및 이를 포함하는 용철제조장치
KR102538769B1 (ko) * 2015-12-03 2023-06-05 주식회사 포스코 스테인리스 스틸 부산물 선별장치 및 이를 이용한 단광 제조방법
KR101674837B1 (ko) * 2015-12-21 2016-11-10 주식회사 포스코 고 p 철광석 사용한 환원철 제조 방법
CN106319209B (zh) * 2016-09-27 2018-08-31 江苏省冶金设计院有限公司 一种转底炉处理铅锌渣提铁工艺
EP3967412A1 (de) * 2020-09-11 2022-03-16 Montanuniversität Leoben Verfahren zum entfernen von flüchtigen bestandteilen aus einem industriestaub, und wertstoff-haltiges produkt
CN114672603B (zh) * 2022-03-11 2022-11-18 北京科技大学 高磷铁矿氢还原-自粉碎提铁除磷方法及装置

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JPH09316512A (ja) * 1996-05-31 1997-12-09 Nkk Corp 酸化鉄ブリケットを副原料として使用する鋼の溶製方法

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AU2012397402B2 (en) 2016-12-15
KR101442920B1 (ko) 2014-09-22
BR112015014606A2 (pt) 2017-07-11
AU2012397402A1 (en) 2015-07-09
EP2937427A4 (en) 2017-03-01
KR20140079224A (ko) 2014-06-26
CN104870660A (zh) 2015-08-26
BR112015014606B1 (pt) 2018-12-04
WO2014098300A1 (ko) 2014-06-26

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