WO2018135351A1 - 溶銑の脱燐方法 - Google Patents
溶銑の脱燐方法 Download PDFInfo
- Publication number
- WO2018135351A1 WO2018135351A1 PCT/JP2018/000325 JP2018000325W WO2018135351A1 WO 2018135351 A1 WO2018135351 A1 WO 2018135351A1 JP 2018000325 W JP2018000325 W JP 2018000325W WO 2018135351 A1 WO2018135351 A1 WO 2018135351A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- dephosphorization
- hot metal
- oxygen source
- agent
- dephosphorizing
- Prior art date
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C1/00—Refining of pig-iron; Cast iron
- C21C1/02—Dephosphorising or desulfurising
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C1/00—Refining of pig-iron; Cast iron
- C21C1/02—Dephosphorising or desulfurising
- C21C1/025—Agents used for dephosphorising or desulfurising
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
- C21C5/28—Manufacture of steel in the converter
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
- C21C5/28—Manufacture of steel in the converter
- C21C5/285—Plants therefor
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Definitions
- the present invention relates to a hot metal dephosphorization method capable of improving dephosphorization efficiency.
- a lime-based dephosphorizing refining agent As a dephosphorizing refining agent for forming a dephosphorizing refining slag, a lime-based dephosphorizing refining agent is generally used. In recent years, it has been demanded to reduce slag generated in a steelmaking process from the viewpoint of environmental protection measures.
- the hot metal dephosphorization process is a low-temperature process advantageous for the dephosphorization reaction, and can therefore be performed with a relatively small amount of slag.
- Such hot metal dephosphorization is performed by adding a dephosphorizing refining agent to the hot metal in the converter and blowing up gaseous oxygen, or by dephosphorizing or dephosphorizing the hot metal in a kneading car or hot metal pan. And a dephosphorizing agent are blown in, and dephosphorization treatment is performed according to the facilities and environment of each steelworks.
- Patent Document 1 by using a CaF 2 medium solvent such as fluorite as a hatching accelerator for a dephosphorizing refining agent, the meltability of the slag for dephosphorizing refining is improved and the dephosphorization efficiency is improved.
- a hot metal dephosphorization method is disclosed.
- the regulation standard of the amount of fluorine eluted from slag has been strengthened from the viewpoint of environmental protection, and it has become necessary to reduce the fluorine concentration to the utmost in dephosphorization slag as well. Therefore, development of a method capable of dephosphorization process molten iron in a high efficiency without using CaF 2 based medium solvent such as fluorite is strongly desired.
- Patent Document 2 uses a converter type furnace while using a dephosphorization medium solvent that does not substantially contain fluorine.
- a method is disclosed in which the slag after dephosphorization treatment is formed as described below to lower the melting point of the slag and to improve the slag drainage after the dephosphorization treatment. 1.
- the slag basicity defined by the mass concentration ratio of CaO and SiO 2 in the slag after the dephosphorization is made 2.5 to 3.5.
- the hot metal temperature after dephosphorization is set to 1320 ° C. or higher and 1380 ° C. or lower. 3.
- the Fe concentration is set to 5% by mass or more.
- Patent Document 3 discloses a dephosphorization method in which a dephosphorization treatment is performed as follows when a hot metal is dephosphorized by adding a dephosphorization medium solvent and top blowing and bottom blowing stirring of oxygen gas. Has been. 1. The bottom blowing stirring power is set to 1.0 kW / t or more. 2. The basicity ((mass% CaO) / (mass% SiO 2 )) of the slag after the treatment is set to 0.6 or more and 2.5 or less. 3. The dephosphorization medium solvent input amount and / or the bottom blowing gas blowing amount is adjusted so that the treatment end point temperature is 1250 ° C. or higher and 1400 ° C. or lower.
- Patent Document 4 describes a dephosphorization treatment method in which a dephosphorization medium solvent mainly composed of a CaO source is added to hot metal in a converter, and oxygen gas is blown from the top blowing lance to the hot metal bath surface.
- a method for dephosphorization is disclosed as follows. 1. The supply rate of oxygen gas from the top blowing lance is set to 1.5 to 5.0 Nm 3 / (min ⁇ molten-ton). 2. A granular dephosphorization medium solvent is applied to the hot metal bath surface from the upper blowing lance so that at least a part of the dephosphorization medium solvent is blown to a fire point generated on the hot metal bath surface by blowing oxygen gas. Spray. 3. The basicity ((mass% CaO) / (mass% SiO 2 )) of the slag after the treatment is adjusted to be 1.0 or more and less than 2.5.
- Patent Document 5 discloses a dephosphorization method as described below. 1. Iron oxide is added to the hot metal held in the hot metal holding container from above the bath surface, and the dephosphorizing agent is blown under the bath surface to dephosphorize the hot metal. 2. Iron oxide is added so that the injection region on the iron oxide bath surface overlaps with 40% or more of the blowing region on the bath surface of the dephosphorizing refining agent in terms of area ratio.
- Patent Documents 2 to 5 can greatly reduce the amount of CaF 2 -based solvent used, but the dephosphorization rate is higher than that when a CaF 2 -based solvent is used. Will drop. That is, the methods disclosed in Patent Documents 2 to 5 have points to be improved in that hot metal dephosphorization is efficiently performed.
- the present invention has been made in view of such a current situation, and an object thereof is to provide a hot metal dephosphorization method capable of improving the hot metal dephosphorization efficiency.
- a hot metal dephosphorization method performed by adding a dephosphorization refining agent to hot metal, wherein the dephosphorization refining agent has a total pore volume within a range of 0.1 ⁇ m to 2.0 ⁇ m in pore diameter.
- a hot metal dephosphorization method comprising a lime-based dephosphorization agent having a sum of 0.1 mL / g or more and an R—CO 2 content of 1% by mass or more.
- the hot metal dephosphorization method according to (1), wherein all of the dephosphorization refining agent is the lime-based dephosphorization agent.
- a lime-based dephosphorization agent is used in which the total pore volume within a predetermined range and the R—CO 2 content are within a specific range.
- FIG. 1 is a schematic cross-sectional view showing a state in which hot metal is dephosphorized using a converter.
- the inventors have made a lime-based dephosphorization in which the sum of the total pore volumes within a pore diameter range of 0.1 ⁇ m or more and 2.0 ⁇ m or less is 0.1 mL / g or more and R—CO 2 is 1% by mass or more.
- the present invention was completed by finding that the use of an agent can improve the dephosphorization efficiency of hot metal.
- the hot metal dephosphorization method according to the present invention will be described using an embodiment in which a converter reactor having a bottom blowing tuyere is used.
- the hot metal dephosphorization method according to the present invention is not limited to a reaction vessel such as a converter, and can also be applied to a hot metal transfer vessel such as a torpedo car or a hot metal ladle.
- FIG. 1 is a schematic cross-sectional view showing a state in which hot metal is dephosphorized using a converter.
- the reaction vessel 10 is a converter type reaction vessel.
- the reaction vessel 10 includes a vessel main body 12 that contains molten iron 20, and an upper blowing lance 14 that adds a gaseous oxygen source 24 such as oxygen gas, a solid oxygen source 26 such as iron oxide, and a dephosphorizing refining agent 28 to the molten iron 20.
- a gaseous oxygen source 24 such as oxygen gas
- a solid oxygen source 26 such as iron oxide
- a dephosphorizing refining agent 28 to the molten iron 20.
- a spout 16 for serving the hot metal 20 after the dephosphorization process is provided.
- a plurality of bottom blowing tuyere 18 for blowing an inert gas 30 into the hot metal 20 is provided at the bottom of the container body 12.
- the hot metal 20 contained in the container body 12 may be hot metal discharged from the blast furnace, and after being discharged from the blast furnace, it is removed by blowing oxygen in the blast furnace casting bed, hot metal transfer container or converter. It may be hot metal that has been treated with silicon.
- the hot metal 20 discharged from the blast furnace and accommodated in the reaction vessel 10 is supplied with a gaseous oxygen source 24 such as oxygen gas and a solid oxygen source 26 such as iron oxide (hereinafter referred to as gaseous oxygen source 24 and solid) from the top blowing lance 14.
- the oxygen source 26 may be collectively referred to as “oxygen source”), and a dephosphorizing agent 28 is added.
- the phosphorous oxide is added to the dephosphorizing slag 22 composed of the dephosphorizing refining agent 28 and the like added from the top blowing lance 14 (hereinafter, the dephosphorizing slag 22 may be referred to as “slag 22”).
- the hot metal 20 is dephosphorized. And calculated from the measured value of the phosphorus concentration of the hot metal 20 discharged from the blast furnace, the dephosphorization oxygen efficiency of the oxygen source obtained empirically, and the phosphorus concentration of the hot metal 20 after the target dephosphorization treatment.
- the addition of the oxygen source from the top blowing lance 14 is stopped to remove the phosphorus. The process ends.
- the hot metal dephosphorization method of the present embodiment among the pores of the lime-based dephosphorization agent, the sum of the total pore volumes having a diameter in the range of 0.1 ⁇ m to 2.0 ⁇ m is 0.1 mL / g or more. And a dephosphorizing agent 28 containing a lime-based dephosphorizing agent having R-CO 2 of 1% by mass or more is used.
- the dephosphorization refining agent 28 the sum of the total pore volumes having a diameter in the range of 0.1 ⁇ m or more and 2.0 ⁇ m or less among the pores is 0.1 mL / g or more, and R—CO 2 is Examples of the dephosphorizing and refining agent that is 1% by mass or more and that is not a lime-based dephosphorizing agent are calcium ferrite and calcium aluminate.
- Lime having a pore diameter in the above range physically improves the wettability between the hot metal and the refining agent, and promotes the penetration of the hot metal into the pores on the surface of the refining agent.
- the surface area of the refining agent in contact with the hot metal is increased, and the decay of CaO described later is further promoted, so that the dephosphorization efficiency is improved.
- hatching of slag is promoted, so that there is much quantity of the lime which exists in the range of 0.1 micrometer or more and 2.0 micrometers or less.
- the sum of the total pore volumes is larger, the slag hatching is promoted and the dephosphorization efficiency is improved. Therefore, the upper limit value of the sum of the total pore volumes does not have to be determined.
- the pore size distribution of the lime-based dephosphorizing agent was measured by the following method. After preliminarily drying lime at 120 ° C. for 4 hours as a pretreatment, a pore distribution having a pore diameter of about 0.0036 to 200 ⁇ m was obtained by mercury porosimetry using an Autopore IV9520 manufactured by Micromerites, and accumulated pores were obtained. A volume curve is calculated. From this cumulative pore volume curve, the total pore volume of pores having a diameter in the range of 0.1 ⁇ m to 2.0 ⁇ m was calculated. The pore diameter was calculated using the following equation (2) which is a Washburn equation.
- P ⁇ D ⁇ 4 ⁇ ⁇ ⁇ cos ⁇ (2)
- P is the pressure (Pa)
- D is the pore diameter ( ⁇ m)
- R—CO 2 is a value indicating the content ratio (mass%) of CO 2 resulting from CaCO 3 remaining in quicklime. When the degree of firing is high, CaCO 3 decreases and the ratio of R—CO 2 decreases. .
- R-CO 2 was calculated by measuring the C concentration in lime with a solid carbon / sulfur analyzer (CS analyzer) and converting it into the amount of CO 2 .
- the dephosphorizing refining agent 28 is preferably added to the same hot metal bath surface as the addition position of the gaseous oxygen source 24. That is, since the above equation (1) is an endothermic reaction, there is a cooling effect of the fire point.
- the dephosphorization reaction is promoted by the effect of cooling the fire point of the lime-based dephosphorizing agent and the effect of promoting the hatching of CaO into the slag 22.
- the in order to increase the surface area of the lime-based dephosphorizing agent and increase the reaction activity of the lime-based dephosphorizing agent when adding to the hot metal bath surface from the top blowing lance 14 together with the carrier gas, the lime-based one having an average particle size of 1 mm or less It is preferable to use a dephosphorizing agent.
- the measuring method of the average particle diameter is as follows.
- Wi is a mass ratio of the particle diameter di, and the particle diameter di is an intermediate diameter of each sieve mesh.
- a lime-based dephosphorizing agent having an average particle size of about 5 to 30 ⁇ m is used. It is preferable.
- a dephosphorizing agent 28 in which quick lime having an R—CO 2 content of 2% by mass or less is appropriately mixed may be used.
- the content ratio of the lime-based dephosphorizing agent to the dephosphorizing refining agent 28 is 50% by mass for the purpose of enhancing the effect of cooling the hot point of the lime-based dephosphorizing agent and the effect of promoting the hatching of CaO into the slag 22.
- the content ratio of the lime-based dephosphorizing agent with respect to the dephosphorizing refining agent 28 is more preferably 100% by mass.
- the slag 22 may be ejected from the furnace port portion by slag forming. It had to be lowered, which was a factor that lowered productivity.
- slag forming is suppressed by the degassing effect by CO 2 generated in the reaction of the above formula (1), so there is no need to reduce the acid feed rate. For this reason, in the hot metal dephosphorization method of the present embodiment, even when hot metal having a Si concentration of 0.4 mass% or more is dephosphorized, dephosphorization treatment can be performed without reducing productivity.
- the basicity ((mass% CaO) / (mass% SiO 2 )) of the slag 22 after the dephosphorization treatment is preferably about 1.8 to 3.5.
- the basicity of the slag 22 after the dephosphorization treatment is lower than 1.8, it is not preferable because the dephosphorization reaction of the hot metal hardly proceeds. Even if the basicity of the slag 22 after dephosphorization is made higher than 3.5, the dephosphorization rate is not improved and the lime cost is increased, which is not preferable.
- An inert gas 30 is blown into the hot metal 20 from the bottom blowing tuyere 18 to stir the hot metal 20.
- the amount of the inert gas 30 blown is preferably 0.02 Nm 3 / (min ⁇ molten-ton) or more.
- too much stirring of the hot metal 20 is not preferable because the rate at which C in the hot metal reduces FeO in the slag 22 is increased and the concentration of FeO contributing to the dephosphorization reaction is reduced.
- the amount of the inert gas 30 blown is 0.5 Nm 3 / (min ⁇ molten-ton) or less.
- the present invention is not limited thereto, and oxygen gas is used instead of the inert gas 30 or together with the inert gas 30. Gas may be blown.
- “Hot metal-ton” in the unit of the blowing amount of the inert gas 30 means the blowing amount of the inert gas 30 per 1 ton of hot metal stored in the reaction vessel 10.
- oxygen gas including industrial pure oxygen
- air oxygen-enriched air
- oxygen gas it is preferable to use oxygen gas.
- oxygen gas By using oxygen gas, the dephosphorization reaction rate can be increased as compared with the case of using other gases.
- a mixed gas it is preferable to increase the oxygen concentration rather than air in order to increase the dephosphorization reaction rate.
- these solid oxygen sources 26 are added by spraying from the top blowing lance 14 to the bath surface of the hot metal 20. Thereby, while being able to improve the oxygen potential of the slag 22, the dephosphorization promotion effect by a hot spot cooling is acquired.
- the solid oxygen source 26 In adding the solid oxygen source 26 from the top blowing lance 14, the solid oxygen source 26 is placed at a position near the bath surface of the hot metal 20 to which the gaseous oxygen source 24 is blown from a supply system different from the supply system of the gaseous oxygen source 24. It is preferable to add.
- the hot spot which is the bath surface position of the hot metal 20 to which the gaseous oxygen source 24 is added, is predominantly decarburized by the gaseous oxygen source 24, and has a high temperature exceeding 2000 ° C. due to heat generation such as the decarburized reaction. .
- the dephosphorization reaction since the dephosphorization reaction is accelerated as the temperature becomes lower in terms of thermodynamics, the dephosphorization reaction substantially occurs in the vicinity of a fire point of approximately 1800 ° C. or less, which is slightly away from the fire point. Become.
- the phosphorus distribution ratio (ratio of phosphorus concentration in the slag to phosphorus concentration in the molten steel), which is an index indicating the dephosphorization ability at 1550 ° C., is approximately twice the phosphorus distribution ratio at 1600 ° C. as a thermodynamic estimate. .
- the upper blow lance 14 having a supply system different from the supply system of the gaseous oxygen source 24 only needs to have at least a double pipe structure, and one of the double pipe structures is connected to the flow of the gaseous oxygen source 24. What is necessary is just to let the other side of a double pipe structure be a flow path of the solid oxygen source 26 as a path
- the gaseous oxygen source 24 may be added from a plurality of lance holes, and the solid oxygen source 26 may be added from a lance hole provided on the central axis.
- the solid oxygen source 26 can be added to the bath surface position surrounded by a plurality of fire points formed by the addition of the gaseous oxygen source 24, and the solid oxygen source It is more preferable because the temperature at the addition position of 26 can be maintained at a high temperature lower than the fire point.
- a plurality of lance holes may be provided along a virtual circle centered on the central axis of the top blowing lance 14, and the gaseous oxygen source 24 and the solid oxygen source 26 may be alternately added from the plurality of lance holes at different times. .
- an amount of a solid oxygen source 26 that can ensure a predetermined FeO concentration in the slag 22 is added in the vicinity of the hot metal bath surface to which the gaseous oxygen source 24 is added. It is preferable.
- the upper limit of the addition amount of the solid oxygen source 26 added in the vicinity of the hot metal bath surface to which the gaseous oxygen source 24 is added is set to an addition amount that does not excessively remove heat from the hot metal 20 according to the equipment specifications. That's fine.
- the solid oxygen source 26 having an addition amount in the range of 1 kg to 2.0 kg in the vicinity of the hot metal bath surface to which the gaseous oxygen source 24 is added. It is more preferable to add an amount of solid oxygen source 26 within the range in the vicinity of the hot metal bath surface to which the gaseous oxygen source 24 is added.
- the addition amount of the solid oxygen source 26 added in the vicinity of the hot metal bath surface to which the gaseous oxygen source 24 is added is less than 0.1 kg with respect to the gaseous oxygen source 24 of 1 Nm 3 , the FeO concentration of the slag 22 Is not preferable because of a low.
- the addition amount of the solid oxygen source 26 is more than 2.0 kg with respect to the gaseous oxygen source 24 of 1 Nm 3 , the amount of heat removal at the hot metal bath surface to which the solid oxygen source 26 is added becomes large, and the slag 22 is not sufficiently hatched. This is not preferable because the dephosphorization efficiency decreases.
- About the solid oxygen source added to positions other than the bath surface position in the vicinity of the hot metal bath surface to which the gaseous oxygen source 24 is added it may be added to the hot metal 20 by a method such as top addition or injection addition.
- the hot metal temperature rises due to the oxidation reaction heat, and when the solid oxygen source 26 is used, the sensible heat, latent heat, and decomposition heat of the solid oxygen source 26 itself are higher than the oxidation reaction heat. Therefore, the hot metal temperature decreases. Therefore, the usage ratio of the gaseous oxygen source 24 and the solid oxygen source 26 is determined by the addition amount of the gaseous oxygen source 24 and the addition amount of the solid oxygen source 26 added in the vicinity of the hot metal bath surface to which the gaseous oxygen source 24 is added. While maintaining this range, it may be set according to the target temperature after the dephosphorization treatment of the hot metal 20.
- the addition amount of the solid oxygen source 26 added to the position near the hot metal bath surface to which the gaseous oxygen source 24 is added is adjusted so that the FeO concentration in the slag 22 is in the range of 10 mass% to 50 mass%. It is preferable. Thereby, the dephosphorization efficiency of the hot metal 20 can be improved. It is more preferable that the FeO concentration in the slag 22 be in the range of 10% by mass to 30% by mass because the dephosphorization efficiency of the hot metal 20 can be further improved.
- the hot metal dephosphorization method of the present embodiment an example in which the inert gas 30 is blown from the bottom blowing tuyere 18 and the hot metal 20 is stirred has been described, but the present invention is not limited thereto.
- the hot metal 20 may be stirred by blowing an inert gas 30 from an injection lance immersed in the hot metal 20.
- the hot metal discharged from the blast furnace was desiliconized in the blast furnace casting floor, then transported in a hot metal ladle with a capacity of 250 tons, desulfurized by a mechanical stirring method, and then dephosphorized using a top blowing lance in a converter. .
- a solid oxygen source 10 kg / (molten iron-ton) of iron sand having an average particle diameter of 500 ⁇ m was added.
- the addition from the top blowing lance by the carrier gas and the top addition from the furnace hopper were used in combination.
- oxygen was added from the top blowing lance at an acid feed rate of 25000 Nm 3 / h.
- the dephosphorizing refining agent 10 kg / (molten-ton) of a dephosphorizing refining agent having an average particle diameter of 2 mm or less was added from a gaseous oxygen source supply system.
- the method for measuring the average particle size of the dephosphorizing agent is as follows. Take 1 kg of dephosphorizing agent, 0.100 mm or less, 0.100 mm to 0.150 mm, 0.150 mm to 0.212 mm, 0.212 mm to 0.250 mm, 0.250 to 0 300mm or less, 0.300mm to 0.355mm or less, 0.355mm to 0.425mm or less, 0.425mm to 0.500mm or less, 0.500mm to 0.600mm or less, 0.600mm to 0 710 mm or less, 0.710 mm to 0.850 mm or less, 0.850 mm to 1.000 mm or less, 1.00 mm or more, and screened in 13 stages, and the average particle size is calculated using the above formula (3). Calculated as a ratio.
- Table 1 shows the content ratio (% by mass) of the lime-based dephosphorizing agent contained in the dephosphorizing agents used in Comparative Examples 1 to 6 and Examples 1 to 28, and the pore diameter of the lime-based dephosphorizing agent of 0.1 ⁇ m.
- the sum (mL / g) of the total pore volume within the range of 2.0 ⁇ m or less, the content ratio (% by mass) of R—CO 2 , the phosphorus concentration (% by mass) of the hot metal before the dephosphorization treatment, The phosphorus concentration (mass%) of the hot metal after the dephosphorization treatment, the dephosphorization rate (%), and the end point temperature (° C.) are shown.
- the dephosphorization rate is a value calculated using the phosphorus concentration of the hot metal before the dephosphorization treatment, the phosphorus concentration of the hot metal after the dephosphorization treatment, and the following equation (4).
- the total pore volume within the range where the pore diameter of the lime-based dephosphorization agent is 0.1 ⁇ m or more and 2.0 ⁇ m or less is less than 0.1 mL / g, or the value of R—CO 2 It is the comparative example which carried out the dephosphorization process using the dephosphorization refining agent containing the lime type
- the total pore volume within the range where the pore diameter of the lime-based dephosphorization agent is 0.1 ⁇ m or more and 2.0 ⁇ m or less is 0.1 mL / g or more, and R—CO 2 is 1% by mass.
- the lime-based desiccation in which the sum of the total pore volumes in the pore diameter range of 0.1 ⁇ m or more and 2.0 ⁇ m or less is 0.1 mL / g or more and R—CO 2 is 1% by mass or more.
- the dephosphorization rates of Examples 17 to 28 were higher than those of Comparative Examples 1 to 6 and Examples 1 to 16. From this, all of the dephosphorization refining agents had a total pore volume in the range of 0.1 ⁇ m or more and 2.0 ⁇ m or less in pore diameter of 0.1 mL / g or more and R—CO 2 of 1% by mass or more. It was confirmed that the dephosphorization efficiency of the hot metal can be further improved in the case of the lime-based dephosphorizing agent.
- the agent can improve the dephosphorization efficiency of the hot metal by the effect of cooling the hot spot and the effect of promoting the hatching of CaO into slag.
- dephosphorizing refining agent that does not contain the lime-based dephosphorizing agent is used by dephosphorizing hot metal using a dephosphorizing refining agent that includes a lime-based dephosphorizing agent that can improve the dephosphorization efficiency of hot metal. Therefore, it can be said that the dephosphorization efficiency can be improved as compared with the case where hot metal dephosphorization is performed.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Botany (AREA)
- Refinement Of Pig-Iron, Manufacture Of Cast Iron, And Steel Manufacture Other Than In Revolving Furnaces (AREA)
- Carbon Steel Or Casting Steel Manufacturing (AREA)
Abstract
Description
1.溶銑を脱燐処理する際に、脱燐処理後のスラグ中のCaOとSiO2との質量濃度比で定義されるスラグ塩基度を2.5以上3.5以下にする。
2.脱燐処理後の溶銑温度を1320℃以上1380℃以下にする。
3.全吹錬時間の60%が経過する前から吹錬終了まで、底吹きガス流量を溶銑1トンあたり0.18Nm3/min以下に保つことで、脱燐処理後のスラグ中T.Fe濃度を5質量%以上にする。
1.底吹き撹拌動力を1.0kW/t以上にする。
2.処理後のスラグの塩基度((質量%CaO)/(質量%SiO2))を0.6以上2.5以下にする。
3.処理終点温度が1250℃以上1400℃以下になるように脱燐用媒溶剤投入量および/または底吹きガス吹き込み量を調整する。
1.上吹きランスからの酸素ガスの供給速度を1.5~5.0Nm3/(min・溶銑-ton)にする。
2.脱燐用媒溶剤のうちの少なくとも一部が、酸素ガスの吹きつけによって溶銑浴面に生じる火点に吹きつけられるように、上吹きランスから粉粒状の脱燐用媒溶剤を溶銑浴面に吹きつける。
3.処理後のスラグの塩基度((質量%CaO)/(質量%SiO2))が1.0以上2.5未満となるように調整する。
1.溶銑保持容器内に保持された溶銑に、その浴面上方から酸化鉄を添加するとともに、浴面下に脱燐精錬剤を吹き込んで溶銑を脱燐処理する。
2.酸化鉄の浴面における投入領域が、面積率で脱燐精錬剤の浴面での吹き出し領域の40%以上とラップするように、酸化鉄を添加する。
(1)脱燐精錬剤を溶銑に添加して行なう溶銑の脱燐方法であって、前記脱燐精錬剤は、細孔径が0.1μm以上2.0μm以下の範囲内の全細孔容積の和が0.1mL/g以上であって、R-CO2が1質量%以上の石灰系脱燐剤を含む、溶銑の脱燐方法。
(2)前記脱燐精錬剤は、前記石灰系脱燐剤を50質量%以上含む、(1)に記載の溶銑の脱燐方法。
(3)前記脱燐精錬剤の全ては、前記石灰系脱燐剤である、(1)に記載の溶銑の脱燐方法。
石灰系脱燐剤の細孔径分布は、以下の方法にて測定した。前処理として石灰を120℃で4時間恒温乾燥を行った後、Micromerities社製のオートポアIV9520を用いて、水銀圧入法により細孔直径約0.0036~200μmの細孔分布を求め、累積細孔容積曲線を算出する。この累積細孔容積曲線から直径0.1μm以上2.0μm以下の範囲内となる細孔の全細孔容積を算出した。細孔径は、Washburnの式である下記(2)式を用いて算出した。
上記(2)式において、Pは圧力(Pa)、Dは細孔直径(μm)、σは水銀の表面張力(=480dynes/cm)、θは水銀と試料との接触角(=140°)である。
脱燐精錬剤28を溶銑20に添加するにあたり、脱燐精錬剤28は、気体酸素源24の添加位置と同一の溶銑浴面に添加することが好ましい。すなわち、上記(1)式は、吸熱反応であるので火点の冷却効果がある。脱燐反応は、熱力学的に低温であるほど反応が促進されるので、石灰系脱燐剤の火点の冷却効果と、CaOのスラグ22への滓化促進効果により脱燐反応が促進される。石灰系脱燐剤の表面積を広げ、石灰系脱燐剤の反応活性を高めることを目的として、上吹きランス14からキャリアガスとともに溶銑浴面に添加する際は、平均粒径1mm以下の石灰系脱燐剤を用いることが好ましい。平均粒径の測定方法は以下の通りである。石灰系脱燐剤を1kg採取し、0.100mm以下、0.100mm超~0.150mm以下、0.150mm超~0.212mm以下、0.212mm超~0.250mm以下、0.250mm超~0.300mm以下、0.300mm超~0.355mm以下、0.355mm超~0.425mm以下、0.425mm超~0.500mm以下、0.500mm超~0.600mm以下、0.600mm超~0.710mm以下、0.710mm超~0.850mm以下、0.850mm超~1.000mm以下、1.000mm超、の13段階に篩分けし、下記(3)式を用いて平均粒径を質量比率で計算した。
12 容器本体
14 上吹きランス
16 出銑口
18 底吹き羽口
20 溶銑
22 スラグ
24 気体酸素源
26 固体酸素源
28 脱燐精錬剤
30 不活性ガス
Claims (3)
- 脱燐精錬剤を溶銑に添加して行なう溶銑の脱燐方法であって、
前記脱燐精錬剤は、細孔径が0.1μm以上2.0μm以下の範囲内の全細孔容積の和が0.1mL/g以上であって、R-CO2が1質量%以上の石灰系脱燐剤を含む、溶銑の脱燐方法。 - 前記脱燐精錬剤は、前記石灰系脱燐剤を50質量%以上含む、請求項1に記載の溶銑の脱燐方法。
- 前記脱燐精錬剤の全ては、前記石灰系脱燐剤である、請求項1に記載の溶銑の脱燐方法。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2018563282A JP6773135B2 (ja) | 2017-01-18 | 2018-01-10 | 溶銑の脱燐方法 |
KR1020197020970A KR102260155B1 (ko) | 2017-01-18 | 2018-01-10 | 용선의 탈인 방법 |
CN202210118003.XA CN114457204B (zh) | 2017-01-18 | 2018-01-10 | 铁水的脱磷方法 |
CN201880007485.3A CN110191968A (zh) | 2017-01-18 | 2018-01-10 | 铁水的脱磷方法 |
BR112019014620-2A BR112019014620B1 (pt) | 2017-01-18 | 2018-01-10 | Método de desfosforação de metal quente |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2017-006360 | 2017-01-18 | ||
JP2017006360 | 2017-01-18 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2018135351A1 true WO2018135351A1 (ja) | 2018-07-26 |
Family
ID=62908652
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2018/000325 WO2018135351A1 (ja) | 2017-01-18 | 2018-01-10 | 溶銑の脱燐方法 |
Country Status (5)
Country | Link |
---|---|
JP (1) | JP6773135B2 (ja) |
KR (1) | KR102260155B1 (ja) |
CN (2) | CN110191968A (ja) |
TW (1) | TWI664294B (ja) |
WO (1) | WO2018135351A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2021188073A (ja) * | 2020-05-27 | 2021-12-13 | Jfeスチール株式会社 | 電気炉による溶鉄の製造方法 |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2021014918A1 (ja) * | 2019-07-22 | 2021-01-28 | Jfeスチール株式会社 | 溶鉄の脱りん方法 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH05294683A (ja) * | 1992-04-13 | 1993-11-09 | Nippon Steel Corp | 生石灰の製造方法 |
JP2004176096A (ja) * | 2002-11-26 | 2004-06-24 | Osaka Koukai Kk | 一次精錬用石灰系フラックス |
JP2007277664A (ja) * | 2006-04-10 | 2007-10-25 | Osaka Koukai Kk | 石灰系精錬用フラックス |
JP2009155161A (ja) * | 2007-12-26 | 2009-07-16 | Nakayama Sekkai Kogyo Kk | 竪形焼成炉による塩焼き生石灰の製造法およびその方法によって製造された塩焼き生石灰 |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS57171610A (en) * | 1981-04-13 | 1982-10-22 | Nippon Steel Corp | Dephosphorizing agent for molten metal and its production |
JP3239197B2 (ja) | 1993-07-05 | 2001-12-17 | 新日本製鐵株式会社 | 転炉製鋼法 |
JP2000282124A (ja) * | 1999-03-29 | 2000-10-10 | Kawasaki Steel Corp | 転炉スラグの改質方法及び改質スラグを用いた溶銑脱りん方法 |
JP2001288507A (ja) | 2000-04-04 | 2001-10-19 | Nkk Corp | 低燐溶銑の製造方法 |
JP4901132B2 (ja) * | 2005-05-31 | 2012-03-21 | Jfeスチール株式会社 | 転炉吹錬方法及び転炉吹錬用上吹きランス |
TW200730636A (en) * | 2005-11-09 | 2007-08-16 | Jef Steel Corp | Dephosphorization process of molten iron |
JP4743078B2 (ja) | 2006-10-24 | 2011-08-10 | 住友金属工業株式会社 | 脱燐処理後のスラグの排滓性向上方法およびそれを用いた溶銑の脱燐処理方法 |
JP5135836B2 (ja) * | 2007-03-19 | 2013-02-06 | Jfeスチール株式会社 | 溶銑の脱燐処理方法 |
JP5181520B2 (ja) | 2007-04-16 | 2013-04-10 | Jfeスチール株式会社 | 溶銑の脱燐処理方法 |
JP2012031452A (ja) * | 2010-07-29 | 2012-02-16 | Jfe Steel Corp | 溶銑の脱燐処理方法 |
EP2796569B1 (en) * | 2011-12-20 | 2017-08-02 | JFE Steel Corporation | Converter steelmaking method |
-
2018
- 2018-01-10 WO PCT/JP2018/000325 patent/WO2018135351A1/ja active Application Filing
- 2018-01-10 JP JP2018563282A patent/JP6773135B2/ja active Active
- 2018-01-10 KR KR1020197020970A patent/KR102260155B1/ko active IP Right Grant
- 2018-01-10 CN CN201880007485.3A patent/CN110191968A/zh active Pending
- 2018-01-10 CN CN202210118003.XA patent/CN114457204B/zh active Active
- 2018-01-15 TW TW107101411A patent/TWI664294B/zh active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH05294683A (ja) * | 1992-04-13 | 1993-11-09 | Nippon Steel Corp | 生石灰の製造方法 |
JP2004176096A (ja) * | 2002-11-26 | 2004-06-24 | Osaka Koukai Kk | 一次精錬用石灰系フラックス |
JP2007277664A (ja) * | 2006-04-10 | 2007-10-25 | Osaka Koukai Kk | 石灰系精錬用フラックス |
JP2009155161A (ja) * | 2007-12-26 | 2009-07-16 | Nakayama Sekkai Kogyo Kk | 竪形焼成炉による塩焼き生石灰の製造法およびその方法によって製造された塩焼き生石灰 |
Non-Patent Citations (1)
Title |
---|
UEDA, MITSURU ET AL.: "Effect of Pore Distribution in Lime on Desulfurization Mechanism of Hot Metal by Solid Lime", TESTU-TO-HAGANE, vol. 75, no. 1, 31 January 1999 (1999-01-31), pages 58 - 65, XP055506125 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2021188073A (ja) * | 2020-05-27 | 2021-12-13 | Jfeスチール株式会社 | 電気炉による溶鉄の製造方法 |
JP7259803B2 (ja) | 2020-05-27 | 2023-04-18 | Jfeスチール株式会社 | 電気炉による溶鉄の製造方法 |
Also Published As
Publication number | Publication date |
---|---|
CN114457204B (zh) | 2024-08-23 |
TW201829788A (zh) | 2018-08-16 |
BR112019014620A2 (pt) | 2020-04-14 |
CN110191968A (zh) | 2019-08-30 |
JP6773135B2 (ja) | 2020-10-21 |
JPWO2018135351A1 (ja) | 2019-11-07 |
KR102260155B1 (ko) | 2021-06-02 |
KR20190099018A (ko) | 2019-08-23 |
CN114457204A (zh) | 2022-05-10 |
TWI664294B (zh) | 2019-07-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5408369B2 (ja) | 溶銑の予備処理方法 | |
JP6743915B2 (ja) | 溶鋼の脱硫処理方法及び脱硫剤 | |
JP6481774B2 (ja) | 溶鉄の脱りん剤、精錬剤および脱りん方法 | |
WO2018135351A1 (ja) | 溶銑の脱燐方法 | |
JP2007154313A (ja) | 溶銑の脱燐処理方法 | |
JP4977874B2 (ja) | 溶銑の脱燐処理方法 | |
JP5408379B2 (ja) | 溶銑の予備処理方法 | |
JP2008063645A (ja) | 製鋼方法 | |
JP2013127089A (ja) | 溶銑予備処理方法 | |
JP3912176B2 (ja) | 低燐溶銑の製造方法 | |
JP2009114489A (ja) | 溶銑の脱燐処理方法 | |
JP4779464B2 (ja) | 低燐溶銑の製造方法 | |
JP6658049B2 (ja) | 溶銑の脱珪処理方法 | |
JP2011058046A (ja) | 溶銑の脱燐処理方法 | |
JP6760399B2 (ja) | 溶銑の脱燐方法及び精錬剤 | |
JP4513340B2 (ja) | 溶銑の脱燐処理方法 | |
JP2016148075A (ja) | 溶銑の精錬方法 | |
JP2010255054A (ja) | 溶銑の脱燐処理方法 | |
JP2005179691A (ja) | 溶銑の脱珪処理方法 | |
JP2006124840A (ja) | 低燐溶銑の製造方法 | |
JP2005264293A (ja) | 真空脱ガス設備における溶鋼の脱硫処理方法 | |
JP2002212616A (ja) | 溶銑脱リンの制御方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 18741841 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2018563282 Country of ref document: JP Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 20197020970 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
REG | Reference to national code |
Ref country code: BR Ref legal event code: B01A Ref document number: 112019014620 Country of ref document: BR |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 18741841 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 112019014620 Country of ref document: BR Kind code of ref document: A2 Effective date: 20190716 |