WO2014098300A1 - Reduced-iron production method and production device - Google Patents
Reduced-iron production method and production device Download PDFInfo
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- 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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- iron
- compacted
- reduced
- mixture
- reduced iron
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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
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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
- C22B1/16—Sintering; Agglomerating
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- 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
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- 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
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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
- 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
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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
- C22B19/00—Obtaining zinc or zinc oxide
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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
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
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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
- C22B4/00—Electrothermal treatment of ores or metallurgical products for obtaining metals or alloys
- C22B4/08—Apparatus
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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
- 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 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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Abstract
Description
본 발명은 환원철 제조방법 및 제조장치에 관한 것으로서, 더욱 상세하게는 철광석내 불순물인 인, 아연 및 알칼리 원소를 다량 함유하는 철광석을 이용하여 환원율이 우수한 환원철을 제조하면서 인, 아연 및 알칼리 원소를 회수하는 환원철 제조방법 및 제조장치에 관한 것이다.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.
고로, 전로 및 전기로 등에서는 용선 또는 용강을 만드는 원료로 환원철이 사용된다.In blast furnaces, converters and electric furnaces, reduced iron is used as a raw material for forming molten iron or molten steel.
환원철은 철광석이나 산화철 등의 산화철원을 탄소질 환원제(이하, "탄재"라고도 함)나 환원성 가스에 의해 환원시킨 것으로서, 환원철을 얻는 방법으로는 주로 직접 제철법이 사용되고 있다.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. Direct iron making is mainly used to obtain reduced iron.
이러한 일반적인 직접 환원철(DRI) 제조공정의 경우 극미분 철광석을 펠렛으로 제조 후 회전 노상로(Rotary Hearth Furnace; RHF)에서 환원을 유도하여 직접환원철을 제조하는 공정이 개발되어 있다.In the case of the general direct reduced iron (DRI) manufacturing process has been developed a process for producing direct reduced iron by inducing reduction in a rotary hearth furnace (RHF) after the production of ultra-fine iron ore into pellets.
예를 들어 회전 노상로를 이용하여 환원철을 제조하는 방법에 대해서는 "환원철 펠렛의 제조 방법 및 선철의 제조 방법(공개특허 10-2010-0043095); 특허문헌 1", "환원철의 제조 방법(공개특허 10-2010-0122946; 특허문헌 2)" 등에서 구체적으로 공지되어 있다.For example, 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);
특허문헌 1 및 특허문헌 2는 모두 회전형 로를 이용하여 환원철을 제조하는 기술에 관한 것으로서, 특히 특허문헌 1은 환원철 제조시 금속화율을 높이는 것을 목적으로 원료의 입도를 관리하여 반응성을 향상시키는 기술이고, 특허문헌 2는 아연을 고농도로 함유하는 철광석으로부터 환원철을 제조하는 기술에 관한 것이다.
종래의 환원철을 제조하는 회전형 로는 밀폐식으로서, 최대 1,350℃의 환원성 분위기에서 철광석을 환원시키기 때문에, 로 내를 환원성 분위기로 제어하는 어려움이 있었고, 생산량이 연산 15만톤 ~ 50만톤 규모의 공정으로서 대량 생산에는 한계가 있었다.Conventional rotary furnaces for producing reduced iron are hermetically sealed and reduce iron ore in a reducing atmosphere of up to 1,350 ° C. Therefore, there is a difficulty in controlling the furnace in a reducing atmosphere, and the production volume is 150,000 to 500,000 tons. Mass production had a limit.
그래서, 환원철의 대량 생산을 위하여 회전형 로의 한계를 넘어서는 새로운 방식의 환원철 제조 방법이 요구되고 있는 실정이다.Thus, there is a need for a new method for producing reduced iron that exceeds the limits of a rotary furnace for mass production of reduced iron.
이에 따라, 종래에는 산화성 분위기의 소성로를 이용하여 부분환원광을 제조하는 공정이 제안되었지만, 소성로 내의 산화성 분위기에 의해 환원제인 탄소가 철광석의 환원제로 사용되는 양보다 주위 분위기의 산소와의 연소에 의한 연소열로 사용되는 양이 상대적으로 더 많아 환원에 이용되는 탄소의 이용률이 낮아 철광석의 환원효율이 낮은 문제가 있었다.Accordingly, in the past, a process for producing a partial reduction ore using an oxidizing atmosphere firing furnace has been proposed, but due to the combustion of oxygen as a reducing agent due to combustion with oxygen in the ambient atmosphere, rather than the amount of carbon used as a reducing agent for iron ore by the oxidizing atmosphere in the firing furnace. There is a problem that the reduction efficiency of iron ore is low because the amount of the heat used for combustion is relatively high and the utilization rate of carbon used for reduction is low.
또한, 산화성 분위기의 소성로를 사용하는 경우 철광석이 환원 후 주위 산화성 분위기에 의해 재산화가 발생함으로서 환원율을 높일 수 없다는 문제가 있었다.In addition, in the case of using a calcination furnace in an oxidizing atmosphere, iron ore has a problem that the reduction rate cannot be increased because reoxidation occurs by the surrounding oxidizing atmosphere.
한편, 철광석 내 함유된 인(P), 아연(Zn) 및 알칼리 산화물(K2O+Na2O)은 최종 제품에 너무 많이 함유되는 경우 각종 결함을 유발하는 불순물로서, 종래에는 이러한 불순물, 즉 인(P), 아연(Zn) 및 알칼리 산화물(K2O+Na2O)이 적게 함유된 철광석을 사용하여 환원철을 생산하였다.On the other hand, 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).
하지만, 근래에는 불순물이 적게 함유된 양질의 철광석 고갈되면서 양질의 철광석 값이 상승하여 양질의 철광석만으로 가지고 환원철을 생산하는데 한계가 있었다. 그래서 제강 공정에서 이러한 불순물을 제거하는 기술이 제안되었지만, 제강공정에서 불순물을 제거하기 위해서는 각종 부원료의 투입 및 불순물 제거를 위한 공정의 추가가 불가피 하였고, 이에 따라 생산 단가가 높아지는 문제가 있었다.However, in recent years, as the depletion of high-quality iron ore containing less impurities, the value of high-quality iron ore is increased, and there is a limit in producing reduced iron with only high-quality iron ore. Thus, a technique of removing such impurities in the steelmaking process has been proposed, but in order to remove impurities in the steelmaking process, it is inevitable to add various subsidiary materials and add a process for removing impurities, thereby increasing production costs.
[선행기술문헌][Preceding technical literature]
[특허문헌][Patent Documents]
(특허문헌 1) 공개특허 10-2010-0043095 (2010. 04. 27)(Patent Document 1) Published Patent 10-2010-0043095 (2010. 04. 27)
(특허문헌 2) 공개특허 10-2010-0122946 (2010. 11. 23)(Patent Document 2) Published Patent 10-2010-0122946 (2010. 11. 23)
본 발명은 산화성 분위기의 개방형 환원로에서 환원철을 제조할 수 있는 환원철 제조방법 및 제조장치를 제공한다.The present invention provides a reduced iron production method and apparatus for producing reduced iron in an open reduction furnace of an oxidizing atmosphere.
특히, 철광석과 탄재를 미리 혼합한 혼합물을 이용하여 괴성광을 성형하고 이를 산화성 분위기의 환원로에서 충분히 환원시킬 수 환원철 제조방법 및 제조장치를 제공한다.In particular, it provides a method and apparatus for producing reduced iron which can form compacted ore using a mixture of iron ore and carbonaceous material in advance and sufficiently reduce it in a reducing furnace in an oxidizing atmosphere.
또한, 본 발명은 인(P) 함량이 높은 철광석, 아연(Zn)이 높은 철광석, 알카리 산화물(K2O+Na2O) 함량이 높은 철광석을 사용하여 환원철을 생산하여 철광석 원료 대상의 폭을 넓힐 수 있는 환원철 제조방법 및 제조장치를 제공한다.In addition, 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 Provided are a manufacturing method and a manufacturing apparatus.
또한, 환원철을 생산하는 과정에서 철광석 중의 인(P), 아연(Zn) 및 알카리 산화물(K2O+Na2O)을 분리하여 회수할 수 있는 환원철 제조방법 및 제조장치를 제공한다.In addition, 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.
본 발명의 일 실시형태에 따른 환원철 제조방법은 인, 아연 및 알칼리 산화물이 함유된 철원료와 탄재를 혼합하여 혼합물을 조성하는 단계와; 상기 혼합물을 괴성광으로 성형하는 단계; 상기 괴성광을 개방형 환원로에서 환원시키면서 괴성광에 함유된 인, 아연 및 알칼리 원소를 분리시키는 단계; 상기 괴성광이 환원된 환원물을 파쇄하여 환원철과 인을 포함하는 슬래그로 분리하는 단계; 상기 분리된 환원철은 괴성화하고, 상기 슬래그는 회수하는 단계를 포함한다.Reduction iron production method according to an embodiment of the present invention 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.
상기 혼합물을 조성하는 단계에서, 상기 혼합물이 인(P): 0.06%이상, 아연(Zn): 0.02%이상 및 알칼리 산화물(K2O+Na2O): 0.1% 이상을 함유하는 것을 특징으로 한다.In the step of forming the mixture, 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).
상기 혼합물을 조성하는 단계에서, 상기 철원료는 인(P) 함유량이 0.06%이상인 철광석, 아연(Zn) 함유량이 0.02%이상인 철광석 및 알칼리 산화물(K2O+Na2O) 함유량이 0.1% 이상인 철광석 중 1종 이상의 철광석이 혼합되는 것을 특징으로 한다.In the step of forming the mixture, 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.
상기 혼합물을 조성하는 단계에서, 상기 탄재는 석탄 및 철강공정에서 발생하는 함탄 더스트 중 1개 이상이 혼합되는 것을 특징으로 한다.In the step of forming the mixture, the carbon material is characterized in that one or more of the coal-containing dust generated in the coal and steel process is mixed.
상기 혼합물을 조성하는 단계에서, 상기 혼합물은 염기도(CaO/SiO2)가 1 이상인 것을 특징으로 한다.In the step of forming the mixture, the mixture is characterized in that the basicity (CaO / SiO2) is at least one.
상기 혼합물을 조성하는 단계에서, 상기 혼합물은 알칼리 산화물의 함량이 0.5% 이상이 되도록 조정되는 것을 특징으로 한다.In the step of forming the mixture, the mixture is characterized in that the content of the alkali oxide is adjusted to 0.5% or more.
상기 혼합물을 조성하는 단계에서, 상기 혼합물에는 염기도 및 알칼리 산화물의 함량을 조절하기 위한 부원료가 더 혼합되고, 상기 부원료는 염기도 조절용으로 CaO가 사용되고, 알칼리 산화물 함량 조절용으로 Na2CO3 및 K2CO3가 사용되는 것을 특징으로 한다.In the step of forming the mixture, 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.
상기 탄재는 전체 혼합물 100중량부에 대하여 10 중량부 이상이 혼합되는 것을 특징으로 한다.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.
상기 괴성광을 개방형 환원로에서 환원시키는 단계에서, 상기 환원로 내부는 산화성 분위기가 유지되되, 상기 괴성광의 환원시 괴성광 내 탄소에 의한 환원으로 발생되는 가스가 상기 괴성광의 주변을 둘러싸면서 가스막을 형성하여 산화성 분위기와 괴성광을 차단시키는 것을 특징으로 한다.In the step of reducing the compacted light in an open reduction furnace, 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.
상기 괴성광을 개방형 환원로에서 환원시키는 단계에서, 상기 괴성광의 소성온도는 1000℃ 이상이고, 상기 괴성광의 환원시간의 최대치는 괴성광 내 탄소(C)가 완전 소모되기 전까지로 제한하는 것을 특징으로 한다.In the step of reducing the compacted light in an open reduction furnace, the calcined temperature of the compacted light is 1000 ℃ 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.
상기 괴성광을 개방형 환원로에서 환원시키는 단계에서, 상기 환원로에서 상기 괴성광에 함유된 아연(Zn)은 기상으로 배가스 내에서 더스트로 회수하고, 회수된 더스트를 수쇄하여 아연산화물(ZnO)로 분리회수하는 공정이 더 이루어지는 것을 특징으로 한다.In the step of reducing the compacted ore in an open reduction furnace, 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.
상기 환원로에서 괴성광의 환원시 발생되는 기화된 아연(Zn)을 배가스와 함께 배출시키고, 기화된 아연(Zn)과 배가스 중의 산소가 반응하여 아연산화물(ZnO)이 생성되며, 상기 아연산화물(ZnO)은 더스트에 포함되어 회수되는 것을 특징으로 한다.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.
회수된 더스트를 수쇄하는 동안 알칼리 원소는 물과 함께 분리회수되는 것을 특징으로 한다.The alkali element is separated and recovered with water during the crushing of the recovered dust.
상기 환원철과 슬래그로 분리하는 단계에서, 상기 환원철과 슬래그는 자성분리기로 분리되는 것을 특징으로 한다.In the separating of the reduced iron and slag, the reduced iron and slag is characterized in that separated by a magnetic separator.
다른 관점으로 본 발명의 일 실시형태에 따른 환원철 제조방법은 철원료와 탄재를 혼합하여 괴성광을 성형한 다음, 상기 괴성광을 개방형 환원로에서 환원시켜 환원철을 생산하는 것을 특징으로 한다.In another aspect, 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.
상기 탄재는 전체 괴성광 100중량부에 대하여 10 중량부 이상을 혼합하여, 상기 괴성광의 환원시 괴성광 내 탄소에 의한 환원으로 발생되는 가스가 상기 괴성광의 주변을 둘러싸면서 가스막을 형성하여 개방형 환원로 내의 산화성 분위기와 괴성광을 차단시키는 것을 특징으로 한다.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.
한편, 본 발명의 일실시예에 따른 환원철 제조장치는 서로 다른 종류의 철광석이 저장되는 다수의 원료 호퍼와; 탄재가 저장되는 탄재 호퍼와; 상기 원료 호퍼 및 탄재 호퍼에서 분출되는 서로 다른 종류의 철광석 및 탄재를 혼합시켜 혼합물을 조성하는 혼합기와; 상기 혼합물을 괴성광으로 성형하는 제 1 성형기와; 상기 괴성광을 환원시키는 산화성 분위기의 개방형 환원로와; 상기 환원로에서 환원된 환원물을 파쇄시키는 파쇄기와; 파쇄된 환원물을 자력에 의해 환원철과 슬래그로 분리시키는 자성분리기와; 상기 환원철을 성형하는 제 2 성형기를 포함한다.On the other hand, the reduced iron manufacturing apparatus according to an embodiment of the present invention 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.
상기 환원로에서 배기되는 배가스 중 더스트를 포집하는 포집기와; 상기 포집기에서 포집된 더스트를 수쇄시켜 아연산화물(Zn)와 알칼리 원소 함유 폐수를 분리시키는 수쇄기를 더 포함한다.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.
본 발명의 실시예에 따르면, 종래 제선공정에서 철광석 내 불순물 함량이 높아 사용이 불가하였던 철광석을 활용하여 산화성 분위기의 개방형 환원로에서 환원철을 대량으로 생산할 수 있는 효과가 있다.According to an embodiment of the present invention, there is an effect that a large amount of reduced iron can be produced in an open reduction furnace in an oxidizing atmosphere by utilizing iron ore, which was previously impossible to use due to high impurities in iron ore in the iron making process.
부연하자면, 철광석과 탄재를 미리 혼합한 혼합물을 이용하여 괴성광을 성형하고 이를 산화성 분위기의 환원로에서 환원시킴에 따라 괴성광 내에서 발생되는 환원가스에 의해 괴성광이 가스층으로 둘러싸이면서 산화성 분위기와 차단되기 때문에 산화성 분위기에서도 괴성광을 충분히 환원시킬 수 효과가 있다.In other words, as 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.
또한, 철광석 내에 함유된 불순물인 인(P), 아연(Zn) 및 알카리 산화물(K2O+Na2O)을 환원과정 중에 유효하게 사용하여 인(P), 아연(Zn) 및 알카리 산화물(K2O+Na2O)을 철로부터 분리 회수할 수 있는 효과가 있다.In addition, phosphorus (P), zinc (Zn) and alkali oxides (K2O + Na2O), which are impurities contained in iron ore, are effectively used during the reduction process, and thus phosphorus (P), zinc (Zn) and alkali oxides (K2O + Na2O). There is an effect that can be separated and recovered from iron.
이에 따라 철광석 원료 대상의 폭을 넓혀 원료 구입 단가를 낮출 수 있고, 더불어 분리 회수된 인(P), 아연(Zn) 및 알카리 산화물(K2O+Na2O)을 재활용할 수 있는 효과가 있다.Accordingly, 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).
도 1은 본 발명의 일실시예에 따른 환원철 제조장치의 구성과 환원철 제조방법을 개략적으로 도시한 도면이고,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,
도 2는 괴성광을 1200℃에서 20분 환원 후 염기도에 따른 슬래그 내 인회수율의 관계를 나타낸 그래프이며,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
도 3은 염기도 1인 괴성광을 1200℃에서 20분 환원 후 괴성광내 알카리 산화물 함량에 따른 슬래그내 인회수율의 관계를 나타낸 그래프이고,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 ℃,
도 4는 개방형 환원로 내의 온도 및 탄재의 혼합량에 따른 괴성광의 금속화율 관계를 보여주는 그래프이다.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.
이하, 첨부된 도면을 참조하여 본 발명의 실시예를 더욱 상세히 설명하기로 한다. 그러나 본 발명은 이하에서 개시되는 실시예에 한정되는 것이 아니라 서로 다른 다양한 형태로 구현될 것이며, 단지 본 실시예들은 본 발명의 개시가 완전하도록 하며, 통상의 지식을 가진 자에게 발명의 범주를 완전하게 알려주기 위해 제공되는 것이다. 도면상에서 동일 부호는 동일한 요소를 지칭한다.Hereinafter, with reference to the accompanying drawings will be described an embodiment of the present invention in more detail. However, the present invention is not limited to the embodiments disclosed below, but will be implemented in various forms, and only the embodiments are intended to complete the disclosure of the present invention, and to those skilled in the art to fully understand the scope of the invention. It is provided to inform you. Like numbers refer to like elements in the figures.
본 발명의 바람직한 설명을 위하여 본 발명의 일실시예에 따른 환원철 제조방법을 구현하는 환원철 제조장치에 대해서 먼저 설명한다.For the preferred description of the present invention will be described first with respect to the reduced iron manufacturing apparatus for implementing the reduced iron manufacturing method according to an embodiment of the present invention.
도 1은 본 발명의 일실시예에 따른 환원철 제조장치의 구성과 환원철 제조방법을 개략적으로 도시한 도면이다.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.
도면에 도시된 바와 같이 본 발명의 일실시예에 따른 환원철 제조장치는 철광석을 파쇄시키는 제 1 파쇄기(11)와; 상기 제 1 파쇄기(11)에서 파쇄된 철광석이 종류별로 구분되어 저장되는 다수의 원료 호퍼(21, 22, 23)와; 석탄과 같은 탄재를 파쇄시키는 제 2 파쇄기(12)와; 상기 제 2 파쇄기(12)에서 파쇄된 탄재가 저장되는 탄재 호퍼(30)와; 상기 원료 호퍼(21, 22, 23) 및 탄재 호퍼(30)에서 분출되는 서로 다른 종류의 철광석 및 탄재를 혼합시켜 혼합물을 조성하는 혼합기(50)와; 상기 혼합물을 괴성광으로 성형하는 제 1 성형기(61)와; 상기 괴성광을 환원시키는 산화성 분위기의 개방형 환원로(70)와; 상기 환원로(70)에서 환원된 환원물을 파쇄시키는 제 3 파쇄기(13)와; 파쇄된 환원물을 자력에 의해 환원철과 슬래그로 분리시키는 자성분리기(80)와; 상기 환원철을 성형하는 제 2 성형기(62)를 포함한다. 그리고, 부원료를 저장하는 하나 이상의 부원료 호퍼(40)와; 상기 환원로에서 배기되는 배가스 중 더스트를 포집하는 포집기(90)와; 상기 포집기(90)에서 포집된 더스트를 수쇄시켜 아연산화물(Zn)와 알칼리 원소 함유 폐수를 분리시키는 수쇄기(100)를 더 포함한다.As shown in the drawing, the reduced iron manufacturing apparatus according to an embodiment of the present invention includes a first crusher 11 for crushing iron ore; A plurality of
상기 개방형 환원로(70)는 내부가 밀폐되지 않고 개방되는 환원로로서, 괴성광을 연속적으로 이송시키면서 괴성광을 가열시킬 수 있다면, 특정 형상에 한정되지 않고 다양한 방식의 환원로가 적용될 수 있다. 예를 들어 개방형 환원로를 설명하자면, 컨베이어 방식으로 괴성광을 이송시키는 이송수단이 구비된다. 그리고, 상기 이송수단의 상부에는 괴성광이 이송되는 영역을 둘러싸서 환원되는 공간을 형성하는 로본체가 구비되고, 상기 로본체의 내부에는 다수의 버너가 구비되어 로본체 내부를 가열시킨다. 또한, 상기 이송수단의 하부에는 상기 로본체의 내부 공기를 흡입하는 석션수단이 구비된다. 그래서 괴성광이 이송수단에 의해 이송되면서 로본체 내에서는 버너의 연소 및 석션수단의 흡입에 의해 괴성광의 상부에서 하부방향으로 열이 공급된다. 이렇게 개방형 환원로를 사용함에 따라 괴성광을 다층으로 적층할 수 있고, 연속적으로 환원을 시킬 수 있어 환원철을 대량으로 생산할 수 있는 것이 다. The
한편, 상기 제 1 성형기(61) 및 제 2 성형기(62)는 쌍롤식 성형기를 사용한다.On the other hand, the
다음으로 상기와 같이 구성되는 환원철 제조장치를 이용하여 환원철을 제조방법에 대하여 설명한다.Next, a method for producing reduced iron using the reduced iron manufacturing apparatus configured as described above will be described.
도 1에 도시된 바와 같이 다양한 종류의 철광석을 제 1 파쇄기(11)에서 파쇄하여 각각의 종류에 따라 다수의 철원료 호퍼(21, 22, 23)에 구분하여 저장한다. 이때 사용되는 철광석은 인(P) 함유량이 0.06%이상인 철광석, 아연(Zn) 함유량이 0.02%이상인 철광석 및 알칼리 산화물(K2O+Na2O) 함유량이 0.1% 이상인 철광석 등이 사용된다. 물론 인, 아연 및 알칼리 산화물은 하나의 철광석에 두 개 이상 함유될 수도 있다.As shown in FIG. 1, various types of iron ore are crushed in the first crusher 11 and stored in a plurality of iron
그리고, 탄소가 함유된 탄재를 제 2 파쇄기(12)에서 파쇄하여 탄재 호퍼(30)에 저장한다. 여기서 탄재는 석탄 및 철강공정에서 발생하는 함탄 더스트 중 1개 이상이 혼합된 것을 사용할 수 있다. 이때 상기 탄재는 반응성을 향상시키기 위하여 그 입도를 0.1mm이하로 제한하는 것이 바람직하다.The carbonaceous material containing carbon is crushed by the
또한, 부원료 호퍼(40)에는 염기도 조절용 부원료 및 알칼리 산화물 함량 조절용 부원료가 함께 또는 구분하여 개별적으로 저장한다. 예를 들어 염기도 조절용 부원료는 CaO가 사용되고, 알칼리 산화물 함량 조절용 부원료는 Na2CO3 및 K2CO3가 사용된다.In addition, the
이렇게 철광석, 탄재 및 부원료가 준비되었다면 각각을 편량하여 혼합기(50)에 장입한 다음 혼합시켜 혼합물을 조성한다.If iron ore, carbonaceous material and subsidiary materials are prepared in this way, each is weighed, charged in the
이때 상기 혼합물은 철광석 및 탄재의 성분에 의해 인(P): 0.06%이상, 아연(Zn): 0.02%이상 및 알칼리 산화물(K2O+Na2O): 0.1% 이상을 함유하는 것이 바람직하다. 다만, 후술되는 괴성광의 환원시 인의 충분한 분리를 위하여 괴성광을 고염기도 및 고 알칼리 상태로 유지시키는 것이 바람직하다. 이에 따라 상기 혼합물의 염기도(CaO/SiO2)를 1 이상으로 조정하면서, 알칼리 산화물의 함량을 0.5% 이상이 되도록 조정하기 위하여 CaO, Na2CO3 및 K2CO3를 적정량 혼합하는 것이 바람직하다. 이렇게 염기도와 알칼리 산화물의 함량을 한정하는 이유는 이후에 도 2 및 3도 3을 참조하여 설명하도록 한다.At this time, 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. However, it is preferable to maintain the compacted light in a high base group and a high alkali state in order to sufficiently separate phosphorus upon reduction of the compacted light described below. Accordingly, while adjusting the basicity (CaO / SiO 2) of the mixture to 1 or more, it is preferable to mix CaO,
상기 조건과 함이 혼합물이 조성되었다면, 혼합물을 제 1 성형기(61)에 투입하여 일정한 크기의 괴성광으로 성형한다. If the mixture with the above conditions is formed, the mixture is put into the
이어서 성형된 괴성광을 개방형 환원로(70)에 장입하여 산화성 분위기 하에서 괴성광 내의 철(Fe)을 환원시키면서 괴성광에 함유된 인, 아연 및 알칼리 원소를 분리시킨다. 여기서 산화성 분위기라 함은 별도의 분위기 조절 없이 대기 중에 노출되는 것을 의미한다.Subsequently, the compacted compacted light is charged into an
환원 과정 중에 이루어지는 반응에 대하여 부연하자면, 괴성광 내의 철산화물은 괴성광 내의 탄소와 하기의 화학식 1와 같이 반응(환원)되면서 철(Fe)과 CO가 발생된다. 이때 발생된 CO는 괴성광 내의 철산화물과 하기의 화학식 2와 같이 반응(환원)되면서 철(Fe)과 CO2가 발생된다. 한편, 이때 발생된 CO2는 괴성광 내의 탄소와 반응하여 CO로 변환되기도 한다. 이렇게 괴성광 내의 산화철과 탄소가 반응하여 생성되는 CO 가스 및 CO2 가스는 괴성광의 외부로 배출되어 괴성광의 주변을 둘러싸면서 가스막을 형성한다. 이러한 가스막이 개방형 환원로(70) 내부의 산화성 분위기와 괴성광을 차단시키는 역할을 함에 따라 개방형 환원로(70)에서 괴성광의 환원이 원활하게 이루어지는 것이다.In detail, the iron oxide in the compacted ore is reacted (reduced) with carbon in the compacted ore as shown in
이때 괴성광 내에서 산화철과 탄소의 반응이 충분히 이루어져서 가스막을 충분히 형성시키기 위하여 괴성광 내에는 충분한 탄소가 함유되는 것이 바람직하다. 이에 따라 본 실시예에서는 탄재의 함량을 전체 혼합물 100중량부에 대하여 10 중량부 이상이 혼합되는 것으로 한정하는 것이 바람직하다.In this case, it is preferable that sufficient carbon is contained in the compacted light in order to sufficiently react the iron oxide and the carbon in the compacted light to sufficiently form the gas film. Accordingly, in the present embodiment, 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.
또한, 괴성광의 개방형 환원로(70)에서 괴성광을 환원시키기 위하여 개방형 환원로(70) 내의 소성온도를 1000℃ 이상으로 유지하는 것이 바람직하다.In addition, in order to reduce the compacted light in the open
도 4는 개방형 환원로 내의 온도 및 탄재의 혼합량에 따른 괴성광의 금속화율 관계를 보여주는 그래프로서, 탄재가 10중량부 이상 함유된 괴성광이 1000℃ 이상에서 금속화가 원활하게 이루어지는 것을 확인할 수 있다.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 ℃ or more.
또한, 상기 괴성광의 환원시간의 최대치는 괴성광 내 탄소가 반응하여 가스막을 형성하여야 하기 때문에 괴성광 내 탄소(C)가 완전 소모되기 전까지로 제한하는 것이 바람직하다.In addition, 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.
이렇게 개방형 환원로(70)에서 괴성광의 환원이 이루어지는 동안, 괴성광에 함유된 인(P)은 괴성광 내의 산소(O) 및 CaO와 반응하여 CaO·(P2O5)와 같은 형태로 슬래그에 포집된다. 그래서 괴성광은 환원철과 슬래그가 섞인 상태가 된다.While the compacted light is reduced in the
그리고, 괴성광 내에 함유된 아연, 즉 아연산화물 및 알칼리 산화물(K2O+Na2O)은 철산화물 보다 낮은 온도에서 먼저 환원되어 배가스와 함께 배출된다.In addition, 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.
이때 괴성광의 환원시 발생되는 기화된 아연(Zn)은 배가스와 함께 배출되면서 배가스 중의 산소가 반응하여 아연산화물(ZnO)이 생성되며, 아연산화물(ZnO)은 더스트에 포함되어 포집기(90)에 의해 포집된다.At this time, 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
또한, 괴성광의 환원시 발생되는 기화된 알칼리 원소는 배가스와 함께 배출되면서 배가스 중의 산소가 반응하여 다시 알칼리 산하물이 생성되며, 알칼리 산화물 역시 더스트에 포함되어 포집기(90)에 의해 포집된다.In addition, 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
이렇게 포집기(90)에 포집된 더스트를 수쇄기(100)에서 수쇄처리하여 조산화아연과 알칼리함유 폐수를 회수하여 재활용한다.The dust collected in the
한편, 환원철과 슬래그가 섞인 괴성광은 제 3 파쇄기(13)에서 파쇄하고, 이를 자성분리기(80)에서 자력에 의해 분리하여 환원철과 슬래그를 분리한다. 그래서 분리된 환원철은 다시 제 2 성형기(62)에서 일정한 크기의 브리켓으로 성형시키고, CaO 및 인함량이 높은 슬래그는 비료 원료 등으로 재활용된다.On the other hand, the compacted iron mixed with reduced iron and slag is crushed in the
[실시예]EXAMPLE
이하 실시예를 사용하여 본 발명을 설명한다.The present invention will be described using the following examples.
실험에 사용된 각 철광석의 화학 조성을 표 1에 나타내었다.Table 1 shows the chemical composition of each iron ore used in the experiment.
인, 아연 및 알카리(Na2O, K2O) 함량이 높은 철광석을 사용하였으며 각 철광석을 혼합하여 인, 아연 및 알카리 함량이 높은 브리켓을 제조하였다. 또한 아연, 인 및 알카리 함량을 최대로 높일 경우에는 시약급의 산화아연, 인산화물 및 알카리 산화물을 첨가하였다. 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. In addition, to increase the zinc, phosphorus and alkali content to the maximum, reagent grade zinc oxide, phosphate and alkali oxides were added.
또한, 비교예로 표 1에와 같이 제선공정에서 일반적으로 사용하는 철광석(철광석C)의 화학조성을 동시에 나타내었다. 표 1에서 보는 바와 같이 일반적으로 제선공정에서 사용되는 철광석C의 경우 통상적으로 인의 경우 약 0.06% 이하, 아연의 경우 약 0.02%이하 및 알카리 산화물의 경우 0.03% 이하이지만, 철광석A 및 철광석B의 경우 인, 아연 및 알카리 산화물이 상대적으로 높은 것을 알 수 있다. In addition, as a comparative example, as shown in Table 1, the chemical composition of iron ore (iron ore C) generally used in the iron making process was simultaneously shown. As shown in Table 1, 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.
표 1
상기 철광석A와 철광성B를 석탄(20중량%)과 혼합하여 동시에 브리켓을 제조하였으며, 염기도(CaO/SiO2) 및 알카리 산화물 함량을 조절시에는 시약급 CaO, K2O, Na2O를 첨가하였다. 그리고, 환원로 모사 조건에서 브리켓 환원 실험을 실시하였다.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.
불활성 가스 분위기하 환원온도는 1200℃, 승온속도는 50℃/min 및 환원온도에서 20분 유지 후 실험을 완료하였으며, 브리켓 내 Fe, Zn, P 및 슬래그내 Fe, Zn, P, K, Na 분석을 실시하였다.The experiment was completed after maintaining the reduction temperature at 1200 ℃, the heating rate at 50 ℃ / 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.
도 2는 괴성광을 1200℃에서 20분 환원 후 염기도에 따른 슬래그 내 인회수율의 관계를 나타낸 그래프이고, 도 3은 염기도 1인 괴성광을 1200℃에서 20분 환원 후 괴성광내 알카리 산화물 함량에 따른 슬래그내 인회수율의 관계를 나타낸 그래프이다.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 ℃ 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 ℃ It is a graph showing the relationship between the yield rate in slag.
도 2에서 알 수 있듯이 염기도 증가와 함께 슬래그로의 인회수율은 소폭 증가하고 있음을 알 수 있다. 인산화물(P2O5)의 경우 고염기도 조건에서 산화물로서 안정화되며, 특히 알카리 산화물과 같이 강염기성 산화물의 소량 첨가시에도 슬래그내 인산화물이 안정화되는 것으로 알려져 있다. 그러므로 인산화물이 산화철의 환원과정에서 환원되어 금속 Fe내로 용해되는 것을 방지하고 슬래그내에 상존시키기 위해서는 고염기도 슬래그 및 알카리 산화물의 소량 첨가가 유효함을 알 수 있다.As can be seen in Figure 2 it can be seen that with increasing the basicity, the yield of slag is slightly increased. Phosphorus oxide (P 2 O 5) is stabilized as an oxide under conditions of high base, and in particular, it is known that the phosphorus in the slag is stabilized even when a small amount of a strong base oxide such as alkali oxide is added. Therefore, in order to prevent the phosphate from being reduced in the reduction process of the iron oxide to be dissolved in the metal Fe and to remain in the slag, it can be seen that the addition of a small amount of the high base and the slag and the alkali oxide is effective.
그리고, 실험 후 브리켓의 환원율은 염기도의 영향을 받지 않고 약 85 ~ 90% 수준이였다. 또한 환원후 슬래그 내 아연함량은 초기 0.1%에서 약 0.004% 수준으로 저하됨을 알 수 있다. 산화아연의 경우 철산화물 보다 저온에서 환원되어 금속 Zn으로 되며, 아연의 경우 높은 증기압을 나타내면서 환원과 동시에 기상의 Zn로 기화되며 배가스내에서 재산화가 되어 ZnO로 외부로 배출된 것으로 확인되었다.And, the reduction rate of the briquettes after the experiment was about 85 ~ 90% level without being affected by the basicity. In addition, it can be seen that the zinc content in the slag after reduction is reduced from the initial 0.1% to about 0.004% level. In the case of zinc oxide, it was reduced at a lower temperature than iron oxide to form metal Zn. In the case of 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.
한편, 도 3에서 알 수 있듯이 브리켓 내 알카리 산화물 함량 증가와 동시에 슬래그로의 인회수율이 증가함을 알 수 있다. 그러므로 알카리 산화물의 함량이 높은 광석과 인 함량이 높은 광석을 혼합 사용시 슬래그내 인회수율 향상에 유리한 것을 알 수 있다. 따라서, 상기 혼합물의 염기도(CaO/SiO2)를 1 이상으로 조정하면서, 알칼리 산화물의 함량을 0.5% 이상이 되도록 조정하면, 인을 원하는 수준 이상의 회수할 수 있는 것을 확인할 수 있었다.On the other hand, as can be seen in Figure 3 it can be seen that the increase in the yield of slag at the same time as the alkali oxide content in the briquettes increases. Therefore, it can be seen that it is advantageous to improve the yield recovery in slag when a mixture of ore having a high alkali oxide content and a high phosphorus content is used. Therefore, when the basicity (CaO / SiO 2) of the mixture was adjusted to 1 or more, the content of alkali oxides was adjusted to 0.5% or more, and it was confirmed that phosphorus could be recovered at a desired level or more.
본 발명을 첨부 도면과 전술된 바람직한 실시예를 참조하여 설명하였으나, 본 발명은 그에 한정되지 않으며, 후술되는 특허청구범위에 의해 한정된다. 따라서, 본 기술분야의 통상의 지식을 가진 자라면 후술되는 특허청구범위의 기술적 사상에서 벗어나지 않는 범위 내에서 본 발명을 다양하게 변형 및 수정할 수 있다.Although the invention has been described with reference to the accompanying drawings and the preferred embodiments described above, the invention is not limited thereto, but is defined by the claims that follow. Accordingly, one of ordinary skill in the art may variously modify and modify the present invention without departing from the spirit of the following claims.
[부호의 설명][Description of the code]
11, 12, 13: 파쇄기 21, 22, 23: 원료 호퍼11, 12, 13:
30: 탄재 호퍼 40: 부원료 호퍼30: charcoal hopper 40: side material hopper
50: 혼합기 61, 62: 성형기50:
70: 개방형 환원로 80: 자성분리기70: open reduction furnace 80: magnetic separator
90: 포집기 100: 수쇄기90: collector 100: crusher
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| BR112015014606-6A BR112015014606B1 (en) | 2012-12-18 | 2012-12-27 | Reduced iron production method and production device |
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| CN106319209A (en) * | 2016-09-27 | 2017-01-11 | 江苏省冶金设计院有限公司 | Iron extracting process of lead and zinc residues treated through rotary hearth furnace |
| CN114672603A (en) * | 2022-03-11 | 2022-06-28 | 北京科技大学 | High-phosphorus iron ore hydrogen reduction-self-pulverizing iron extraction and phosphorus removal method and device |
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| KR101626602B1 (en) * | 2014-12-05 | 2016-06-01 | 주식회사 포스코 | Method for compacting fine reduced irons, apparatus for compacting fine reduced irons, and apparatus for manufacturing molten iron comprising the same |
| KR102538769B1 (en) * | 2015-12-03 | 2023-06-05 | 주식회사 포스코 | Sorting device for by-products from producing process of stainless steel and method of producing briquette using the same |
| KR101674837B1 (en) * | 2015-12-21 | 2016-11-10 | 주식회사 포스코 | Method for reducing iron ore containing hihg p |
| EP3967412A1 (en) * | 2020-09-11 | 2022-03-16 | Montanuniversität Leoben | Method for removing volatile components from industrial dust and resulting valuable product obtained |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3443931A (en) * | 1965-09-10 | 1969-05-13 | Midland Ross Corp | Process for making metallized pellets from iron oxide containing material |
| JPH11131119A (en) * | 1997-10-23 | 1999-05-18 | Kobe Steel Ltd | Production of metallic iron and apparatus therefor |
| KR20000062353A (en) * | 1996-12-27 | 2000-10-25 | 구마모토 마사히로 | Production method of metallic iron |
| KR100516507B1 (en) * | 1996-03-15 | 2005-11-25 | 가부시키 가이샤 고베세이코쇼 | Method and apparatus for making metallic iron |
| JP2010007163A (en) * | 2008-06-30 | 2010-01-14 | Sumitomo Metal Ind Ltd | Method for producing reduced iron agglomerate for steel-making |
| KR20100043095A (en) | 2007-09-14 | 2010-04-27 | 신닛뽄세이테쯔 카부시키카이샤 | Process for producing reduced iron pellets, and process for producing pig iron |
| KR20100122946A (en) | 2008-04-25 | 2010-11-23 | 제이에프이 스틸 가부시키가이샤 | Process for production of direct-reduced iron |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3953196A (en) * | 1974-04-05 | 1976-04-27 | Obenchain Richard F | Process for the direct reduction of metal oxides |
| JPH09316512A (en) * | 1996-05-31 | 1997-12-09 | Nkk Corp | Steel melting method using iron oxide briquette as auxiliary material |
| WO2001018256A1 (en) * | 1999-09-06 | 2001-03-15 | Nkk Corporation | Method and facilities for metal smelting |
| CN100510120C (en) * | 2006-05-12 | 2009-07-08 | 万天骥 | Method for producing metallized iron-smelting raw material |
| JP5466590B2 (en) * | 2009-07-21 | 2014-04-09 | 株式会社神戸製鋼所 | Reduced iron manufacturing method using carbonized material agglomerates |
| KR101220554B1 (en) * | 2010-12-28 | 2013-01-10 | 주식회사 포스코 | Apparatus for Manufacturing Molten Iron and Method for Manufacturing Molten Iron Using the Apparatus |
-
2012
- 2012-12-18 KR KR1020120148940A patent/KR101442920B1/en active Active
- 2012-12-27 WO PCT/KR2012/011650 patent/WO2014098300A1/en not_active Ceased
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Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3443931A (en) * | 1965-09-10 | 1969-05-13 | Midland Ross Corp | Process for making metallized pellets from iron oxide containing material |
| KR100516507B1 (en) * | 1996-03-15 | 2005-11-25 | 가부시키 가이샤 고베세이코쇼 | Method and apparatus for making metallic iron |
| KR20000062353A (en) * | 1996-12-27 | 2000-10-25 | 구마모토 마사히로 | Production method of metallic iron |
| JPH11131119A (en) * | 1997-10-23 | 1999-05-18 | Kobe Steel Ltd | Production of metallic iron and apparatus therefor |
| KR20100043095A (en) | 2007-09-14 | 2010-04-27 | 신닛뽄세이테쯔 카부시키카이샤 | Process for producing reduced iron pellets, and process for producing pig iron |
| KR20100122946A (en) | 2008-04-25 | 2010-11-23 | 제이에프이 스틸 가부시키가이샤 | Process for production of direct-reduced iron |
| JP2010007163A (en) * | 2008-06-30 | 2010-01-14 | Sumitomo Metal Ind Ltd | Method for producing reduced iron agglomerate for steel-making |
Non-Patent Citations (1)
| Title |
|---|
| See also references of EP2937427A4 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106319209A (en) * | 2016-09-27 | 2017-01-11 | 江苏省冶金设计院有限公司 | Iron extracting process of lead and zinc residues treated through rotary hearth furnace |
| CN114672603A (en) * | 2022-03-11 | 2022-06-28 | 北京科技大学 | High-phosphorus iron ore hydrogen reduction-self-pulverizing iron extraction and phosphorus removal method and device |
| CN114672603B (en) * | 2022-03-11 | 2022-11-18 | 北京科技大学 | Hydrogen reduction of high phosphorus iron ore - self-crushing iron extraction and phosphorus removal method and device |
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| AU2012397402B2 (en) | 2016-12-15 |
| KR20140079224A (en) | 2014-06-26 |
| EP2937427A1 (en) | 2015-10-28 |
| EP2937427A4 (en) | 2017-03-01 |
| CN104870660A (en) | 2015-08-26 |
| AU2012397402A1 (en) | 2015-07-09 |
| BR112015014606B1 (en) | 2018-12-04 |
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