WO2014098300A1 - Procédé et dispositif de production de fer réduit - Google Patents

Procédé et dispositif de production de fer réduit Download PDF

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Publication number
WO2014098300A1
WO2014098300A1 PCT/KR2012/011650 KR2012011650W WO2014098300A1 WO 2014098300 A1 WO2014098300 A1 WO 2014098300A1 KR 2012011650 W KR2012011650 W KR 2012011650W WO 2014098300 A1 WO2014098300 A1 WO 2014098300A1
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WIPO (PCT)
Prior art keywords
iron
compacted
reduced
mixture
reduced iron
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PCT/KR2012/011650
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English (en)
Korean (ko)
Inventor
손상한
조병국
정해권
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(주)포스코
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Application filed by (주)포스코 filed Critical (주)포스코
Priority to EP12890530.4A priority Critical patent/EP2937427B1/fr
Priority to AU2012397402A priority patent/AU2012397402B2/en
Priority to CN201280077819.7A priority patent/CN104870660A/zh
Priority to BR112015014606-6A priority patent/BR112015014606B1/pt
Publication of WO2014098300A1 publication Critical patent/WO2014098300A1/fr

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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00Preliminary treatment of ores or scrap
    • C22B1/14Agglomerating; Briquetting; Binding; Granulating
    • C22B1/24Binding; Briquetting ; Granulating
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00Preliminary treatment of ores or scrap
    • C22B1/14Agglomerating; Briquetting; Binding; Granulating
    • C22B1/16Sintering; Agglomerating
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21BMANUFACTURE OF IRON OR STEEL
    • C21B13/00Making spongy iron or liquid steel, by direct processes
    • C21B13/006Starting from ores containing non ferrous metallic oxides
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21BMANUFACTURE OF IRON OR STEEL
    • C21B13/00Making spongy iron or liquid steel, by direct processes
    • C21B13/10Making spongy iron or liquid steel, by direct processes in hearth-type furnaces
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00Preliminary treatment of ores or scrap
    • C22B1/14Agglomerating; Briquetting; Binding; Granulating
    • C22B1/24Binding; Briquetting ; Granulating
    • C22B1/242Binding; Briquetting ; Granulating with binders
    • C22B1/244Binding; Briquetting ; Granulating with binders organic
    • C22B1/245Binding; Briquetting ; Granulating with binders organic with carbonaceous material for the production of coked agglomerates
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B19/00Obtaining zinc or zinc oxide
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B26/00Obtaining alkali, alkaline earth metals or magnesium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B4/00Electrothermal treatment of ores or metallurgical products for obtaining metals or alloys
    • C22B4/08Apparatus
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B5/00General methods of reducing to metals
    • C22B5/02Dry methods smelting of sulfides or formation of mattes
    • C22B5/10Dry methods smelting of sulfides or formation of mattes by solid carbonaceous reducing agents

Definitions

  • the present invention relates to a method and apparatus for producing reduced iron, and more particularly, to recover phosphorus, zinc and alkali elements while producing reduced iron having excellent reduction rate by using iron ore containing a large amount of phosphorus, zinc and alkali elements as impurities in iron ore. It relates to a reduced iron production method and a manufacturing apparatus.
  • reduced iron is used as a raw material for forming molten iron or molten steel.
  • Reduced iron is a source of reduced iron oxides such as iron ore or iron oxide with a carbonaceous reducing agent (hereinafter referred to as " coal ash ”) or a reducing gas.
  • coal ash carbonaceous reducing agent
  • Direct iron making is mainly used to obtain reduced iron.
  • a method of manufacturing reduced iron using a rotary hearth furnace is "a method for producing reduced iron pellets and a method for producing pig iron (published patent 10-2010-0043095); Patent Literature 1", “Method for producing reduced iron (published patent) 10-2010-0122946; Patent Document 2) and the like.
  • Patent Document 1 and Patent Document 2 both relate to a technique for producing reduced iron using a rotary furnace, and in particular, Patent Document 1 is a technique for improving the reactivity by managing the particle size of the raw material for the purpose of increasing the metallization rate in the production of reduced iron
  • Patent Document 2 relates to a technique for producing reduced iron from iron ore containing zinc at a high concentration.
  • iron ore has a problem that the reduction rate cannot be increased because reoxidation occurs by the surrounding oxidizing atmosphere.
  • phosphorus (P), zinc (Zn) and alkali oxides (K 2 O + Na 2 O) contained in the iron ore is an impurity that causes various defects when contained in the final product too, conventionally such impurities, that is, phosphorus (P) Reduced iron was produced using iron ore containing less zinc (Zn) and alkali oxides (K2O + Na2O).
  • Patent Document 1 Published Patent 10-2010-0043095 (2010. 04. 27)
  • Patent Document 2 Published Patent 10-2010-0122946 (2010. 11. 23)
  • the present invention provides a reduced iron production method and apparatus for producing reduced iron in an open reduction furnace of an oxidizing atmosphere.
  • the present invention produces reduced iron using iron ore high in phosphorus (P) content, iron ore high in zinc (Zn), iron ore high in alkali oxide (K 2 O + Na 2 O) content to reduce the iron ore raw material can be widened
  • P phosphorus
  • Zn zinc
  • K 2 O + Na 2 O alkali oxide
  • the present invention provides a reduced iron production method and apparatus for separating and recovering phosphorus (P), zinc (Zn) and alkali oxides (K 2 O + Na 2 O) in the iron ore production process.
  • Reduction iron production method comprises the steps of mixing the iron material and carbonaceous material containing phosphorus, zinc and alkali oxides to form a mixture; Shaping the mixture into compacted light; Separating phosphorous, zinc and alkali elements contained in the compacted light while reducing the compacted light in an open reduction furnace; Crushing the reduced product of the compacted ore into a slag including reduced iron and phosphorus; The separated reduced iron is compacted and the slag is recovered.
  • the mixture is characterized in that it contains at least 0.06% phosphorus (P), at least 0.02% zinc (Zn) and at least 0.1% alkali oxide (K 2 O + Na 2 O).
  • the iron raw material is at least one of iron ore with a phosphorus (P) content of 0.06% or more, iron ore with a zinc (Zn) content of 0.02% or more and iron ore having an alkali oxide (K2O + Na2O) content of 0.1% or more It is characterized in that the above iron ore is mixed.
  • the carbon material is characterized in that one or more of the coal-containing dust generated in the coal and steel process is mixed.
  • the mixture is characterized in that the basicity (CaO / SiO2) is at least one.
  • the mixture is characterized in that the content of the alkali oxide is adjusted to 0.5% or more.
  • the mixture is further mixed with a subsidiary material for adjusting the basicity and the content of the alkali oxide
  • the secondary raw material is characterized in that CaO is used for the basicity control, Na2CO3 and K2CO3 is used for the alkali oxide content control It is done.
  • the carbonaceous material is characterized in that 10 parts by weight or more are mixed with respect to 100 parts by weight of the total mixture.
  • the inside of the reduction furnace is maintained in an oxidizing atmosphere, the gas generated by the reduction of carbon in the compacted light when reducing the compacted light surrounds the gaseous film surrounding the vicinity of the compacted light It is characterized by blocking the oxidative atmosphere and compacted light.
  • the calcined temperature of the compacted light is 1000 °C or more
  • the maximum value of the reduced time of the compacted light is characterized in that until the carbon (C) in the compacted light is completely consumed do.
  • zinc (Zn) contained in the compacted ore in the reduction furnace is recovered as dust in exhaust gas in a gaseous phase, and the recovered dust is converted into zinc oxide (ZnO). Separation recovery is characterized in that the process is further made.
  • the vaporized zinc (Zn) generated during the reduction of the compacted light in the reduction furnace is discharged together with the exhaust gas, the zinc oxide (ZnO) is generated by the reaction of the vaporized zinc (Zn) and oxygen in the exhaust gas, the zinc oxide (ZnO) ) Is included in the dust and is recovered.
  • the alkali element is separated and recovered with water during the crushing of the recovered dust.
  • the reduced iron and slag In the separating of the reduced iron and slag, the reduced iron and slag is characterized in that separated by a magnetic separator.
  • the reduced iron manufacturing method according to an embodiment of the present invention is characterized in that the iron raw material and the carbon material is mixed to form a compacted ore, and the reduced ore is reduced in an open reduction furnace to produce reduced iron.
  • the carbonaceous material is mixed with 10 parts by weight or more based on 100 parts by weight of the total compacted light, and the gas generated by the reduction of the compacted light by carbon in the reduction of the compacted light forms a gas film surrounding the vicinity of the compacted light to form an open reduction furnace It is characterized by blocking the oxidizing atmosphere in the inside and the compacted light.
  • the reduced iron manufacturing apparatus and a plurality of raw material hopper that stores different kinds of iron ore; A carbon material hopper in which carbon material is stored; A mixer which forms a mixture by mixing different kinds of iron ore and carbon material ejected from the raw material hopper and the carbon material hopper; A first molding machine for molding the mixture into compacted light; An open reduction furnace of an oxidative atmosphere for reducing the compacted light; A crusher for crushing the reduced product reduced in the reduction furnace; A magnetic separator for separating the pulverized reducing product into reduced iron and slag by magnetic force; And a second molding machine for molding the reduced iron.
  • a collector for collecting dust in the exhaust gas exhausted from the reduction furnace It further comprises a hydride group for crushing the dust collected in the collector to separate the zinc oxide (Zn) and the alkaline element-containing waste water.
  • the compacted light is formed by using a mixture of iron ore and carbon material in advance, the compacted light is reduced in an oxidizing atmosphere, and the compacted gas is surrounded by the gas layer by the reducing gas generated in the compacted light. Since it is blocked, there is an effect that the compacted light can be sufficiently reduced even in an oxidizing atmosphere.
  • the width of the iron ore raw material can be widened, thereby lowering the raw material purchase cost and recycling the separated and recovered phosphorus (P), zinc (Zn) and alkali oxides (K2O + Na2O).
  • FIG. 1 is a view schematically showing a configuration of a reduced iron manufacturing apparatus and a reduced iron manufacturing method according to an embodiment of the present invention
  • Figure 2 is a graph showing the relationship between the phosphorus recovery in the slag according to the basicity after reducing the compacted light at 1200 °C 20 minutes,
  • Figure 3 is a graph showing the relationship between the phosphorus yield in the slag according to the alkali oxide content in the compacted light after reducing the compacted light having a basicity of 20 minutes at 1200 °C,
  • Figure 4 is a graph showing the relationship between the metallization rate of the compacted light according to the temperature and the amount of coal ash mixture in the open reduction furnace.
  • FIG. 1 is a view schematically showing a configuration of a reduced iron manufacturing apparatus and a reduced iron manufacturing method according to an embodiment of the present invention.
  • the reduced iron manufacturing apparatus includes a first crusher 11 for crushing iron ore; A plurality of raw material hoppers 21, 22, and 23 in which the iron ore crushed in the first crusher 11 is classified and stored according to types; A second crusher 12 for crushing carbonaceous material such as coal; A carbon material hopper 30 in which carbon material crushed by the second crusher 12 is stored; A mixer 50 for mixing iron ore and carbon materials of different types ejected from the raw material hoppers 21, 22, and 23 and the carbon material hopper 30 to form a mixture; A first molding machine (61) for molding the mixture into compacted light; An open type reduction furnace 70 in an oxidative atmosphere for reducing the compacted light; A third crusher (13) for crushing the reduced product reduced in the reduction furnace (70); A magnetic separator (80) separating the crushed reduced product into reduced iron and slag by magnetic force; And a second molding machine 62 for molding the reduced iron.
  • a first crusher 11 for crushing iron ore
  • a plurality of raw material hoppers 21, 22, and 23 in which the iron ore crushed in the
  • At least one secondary raw material hopper 40 for storing the secondary raw material;
  • a collector 90 for collecting dust in the exhaust gas exhausted from the reduction furnace;
  • a crusher 100 for crushing the dust collected by the collector 90 to separate the zinc oxide (Zn) and the alkaline element-containing waste water.
  • the open reduction furnace 70 is a reduction furnace in which the inside is not sealed and is open. If the compacted light can be heated while continuously transferring the compacted light, the reducing furnace of various types may be applied without being limited to a specific shape.
  • a conveying means for conveying the compacted light by a conveyor method is provided.
  • the upper part of the conveying means is provided with a main body to form a space that is reduced to surround the area in which the compacted light is transferred
  • the inside of the main body is provided with a plurality of burners to heat the inside of the main body.
  • the lower portion of the transfer means is provided with suction means for sucking the internal air of the main body.
  • the compacted light is transferred by the conveying means, heat is supplied from the upper portion of the compacted light to the lower direction by combustion of the burner and suction of the suction means in the main body.
  • the compacted light can be laminated in multiple layers, and the reduction can be continuously performed, thereby producing a large amount of reduced iron.
  • the first molding machine 61 and the second molding machine 62 uses a twin roll molding machine.
  • the iron ore used is an iron ore having a phosphorus (P) content of 0.06% or more, an iron ore having a zinc (Zn) content of 0.02% or more, and an iron ore having an alkali oxide (K2O + Na2O) content of 0.1% or more.
  • P phosphorus
  • Zn zinc
  • K2O + Na2O alkali oxide
  • phosphorus, zinc and alkali oxides may be contained in more than one iron ore.
  • the carbonaceous material containing carbon is crushed by the second crusher 12 and stored in the carbonaceous material hopper 30.
  • the carbon material may be a mixture of one or more of the coal-containing dust generated in the coal and steel processes.
  • the carbon material is preferably limited to the particle size less than 0.1mm in order to improve the reactivity.
  • the subsidiary hopper 40 stores the basicity adjusting subsidiary materials and alkali oxide content adjusting subsidiary materials together or separately and separately.
  • CaO is used as the basic ingredient for controlling the basicity
  • Na 2 CO 3 and K 2 CO 3 are used as the auxiliary raw materials for adjusting the alkali oxide content.
  • the mixture preferably contains phosphorus (P): 0.06% or more, zinc (Zn): 0.02% or more and alkali oxides (K2O + Na2O): 0.1% or more, depending on the components of iron ore and carbonaceous material.
  • P phosphorus
  • Zn zinc
  • alkali oxides K2O + Na2O
  • the basicity (CaO / SiO 2) of the mixture to 1 or more
  • the reason for limiting the content of basicity and alkali oxide will be described later with reference to FIGS. 2 and 3.
  • the mixture is put into the first molding machine 61 to be molded into a compact size of compacted light.
  • the compacted compacted light is charged into an open reduction furnace 70 to separate phosphorous, zinc and alkali elements contained in the compacted light while reducing iron (Fe) in the compacted light under an oxidizing atmosphere.
  • oxidizing atmosphere means exposure to the atmosphere without additional atmosphere control.
  • the iron oxide in the compacted ore is reacted (reduced) with carbon in the compacted ore as shown in Chemical Formula 1 below to generate iron (Fe) and CO.
  • the generated CO is reacted (reduced) with the iron oxide in the compacted light as shown in Formula 2 below to generate iron (Fe) and CO 2.
  • the generated CO 2 may be converted to CO by reacting with the carbon in the compacted light.
  • the CO gas and the CO 2 gas generated by the reaction of iron oxide and carbon in the compacted light are discharged to the outside of the compacted light to form a gas film while surrounding the vicinity of the compacted light.
  • the gas film serves to block the oxidative atmosphere and the compacted light in the open reduction furnace 70, the compacted light is smoothly reduced in the open reduction furnace 70.
  • the content of the carbonaceous material it is preferable to limit the content of the carbonaceous material to 10 parts by weight or more based on 100 parts by weight of the total mixture.
  • the firing temperature in the open type reducing furnace 70 it is preferable to maintain the firing temperature in the open type reducing furnace 70 at 1000 ° C or more.
  • FIG. 4 is a graph showing the relationship between the metallization rate of the compacted light according to the temperature in the open reduction furnace and the mixing amount of the carbonaceous material, it can be confirmed that the compacted light containing 10 parts by weight or more of the carbonized material is smoothly at 1000 °C or more.
  • the maximum value of the reduction time of the compacted light is preferably limited until the carbon in the compacted light is completely consumed because carbon in the compacted light must react to form a gas film.
  • zinc contained in the compacted light that is, zinc oxide and alkali oxide (K 2 O + Na 2 O) is first reduced at a lower temperature than iron oxide and is discharged together with the exhaust gas.
  • the vaporized zinc (Zn) generated during the reduction of the compacted light is discharged together with the exhaust gas to produce zinc oxide (ZnO) by the reaction of oxygen in the exhaust gas, the zinc oxide (ZnO) is contained in the dust by the collector 90 Is collected.
  • the vaporized alkali element generated upon reduction of the compacted light is discharged together with the exhaust gas to react with oxygen in the exhaust gas to produce an alkali acid product, and the alkali oxide is also included in the dust and collected by the collector 90.
  • the dust collected in the collector 90 is crushed in the crusher 100 to recover the crude zinc oxide and the alkali-containing wastewater.
  • the compacted iron mixed with reduced iron and slag is crushed in the third crusher 13, and separated by magnetic force in the magnetic separator 80 to separate the reduced iron and slag.
  • the separated reduced iron is again formed into a briquette of a constant size in the second molding machine 62, and the slag with high CaO and phosphorus content is recycled as a fertilizer raw material.
  • Table 1 shows the chemical composition of each iron ore used in the experiment.
  • Iron ores with high phosphorus, zinc and alkali (Na 2 O, K 2 O) contents were used, and briquettes with high phosphorus, zinc and alkali contents were prepared by mixing the iron ores.
  • reagent grade zinc oxide, phosphate and alkali oxides were added to increase the zinc, phosphorus and alkali content to the maximum.
  • iron ore C generally used in the iron making process
  • iron ore C generally used in the iron making process is usually about 0.06% or less for phosphorus, about 0.02% or less for zinc and 0.03% or less for alkali oxides, but for iron ore A and iron ore B. It can be seen that phosphorus, zinc and alkali oxides are relatively high.
  • the iron ore A and iron ore B was mixed with coal (20% by weight) to prepare a briquette at the same time, and when adjusting the basicity (CaO / SiO 2) and alkali oxide content, reagent grade CaO, K 2 O, and Na 2 O were added. And the briquette reduction experiment was performed on reduction furnace simulation conditions.
  • the experiment was completed after maintaining the reduction temperature at 1200 °C, the heating rate at 50 °C / min and the reducing temperature for 20 minutes in an inert gas atmosphere, and analyzed Fe, Zn, P in the briquette and Fe, Zn, P, K, Na in the slag. Was carried out.
  • Figure 2 is a graph showing the relationship between the phosphorus yield in the slag according to the basicity after reducing the compacted light at 1200 °C for 20 minutes
  • Figure 3 is according to the alkali oxide content in the compacted light after reducing the compacted light having a basicity of 20 minutes at 1200 °C
  • It is a graph showing the relationship between the yield rate in slag.
  • the reduction rate of the briquettes after the experiment was about 85 ⁇ 90% level without being affected by the basicity.
  • the zinc content in the slag after reduction is reduced from the initial 0.1% to about 0.004% level.
  • zinc oxide it was reduced at a lower temperature than iron oxide to form metal Zn.
  • zinc it was confirmed that it was vaporized into Zn in the gaseous phase at the same time as reduction, and reoxidized in exhaust gas and discharged to ZnO.
  • charcoal hopper 40 side material hopper

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  • Manufacturing & Machinery (AREA)
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  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
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  • Life Sciences & Earth Sciences (AREA)
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Abstract

La présente invention concerne un procédé et un dispositif de production de fer réduit et, plus précisément, un procédé et un dispositif de réduction de fer réduit permettant la production de fer réduit présentant un niveau exceptionnel de réduction, et ce, en utilisant du minerai de fer contenant de grandes quantités d'impuretés telles que du phosphore, du zinc et des éléments alcalins, cela s'accompagnant, dans le même temps, du recueil desdits phosphore, zinc et éléments alcalins.
PCT/KR2012/011650 2012-12-18 2012-12-27 Procédé et dispositif de production de fer réduit WO2014098300A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP12890530.4A EP2937427B1 (fr) 2012-12-18 2012-12-27 Procédé de production de fer réduit
AU2012397402A AU2012397402B2 (en) 2012-12-18 2012-12-27 Reduced-iron production method and production device
CN201280077819.7A CN104870660A (zh) 2012-12-18 2012-12-27 还原铁制造方法及制造设备
BR112015014606-6A BR112015014606B1 (pt) 2012-12-18 2012-12-27 método de produção de ferro reduzido e dispositivo de produção

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2012-0148940 2012-12-18
KR1020120148940A KR101442920B1 (ko) 2012-12-18 2012-12-18 환원철 제조방법 및 제조장치

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WO2014098300A1 true WO2014098300A1 (fr) 2014-06-26

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EP (1) EP2937427B1 (fr)
KR (1) KR101442920B1 (fr)
CN (1) CN104870660A (fr)
AU (1) AU2012397402B2 (fr)
BR (1) BR112015014606B1 (fr)
WO (1) WO2014098300A1 (fr)

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CN106319209A (zh) * 2016-09-27 2017-01-11 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
CN114672603A (zh) * 2022-03-11 2022-06-28 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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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
EP3967412A1 (fr) * 2020-09-11 2022-03-16 Montanuniversität Leoben Procédé d'élimination des composants volatiles d'une poussière industrielle et produit contenant des substances de valeur

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KR20140079224A (ko) 2014-06-26
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AU2012397402B2 (en) 2016-12-15
EP2937427A1 (fr) 2015-10-28
EP2937427B1 (fr) 2020-08-05
CN104870660A (zh) 2015-08-26
AU2012397402A1 (en) 2015-07-09
EP2937427A4 (fr) 2017-03-01

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