WO2014112432A1 - 転炉製鋼法 - Google Patents
転炉製鋼法 Download PDFInfo
- Publication number
- WO2014112432A1 WO2014112432A1 PCT/JP2014/050290 JP2014050290W WO2014112432A1 WO 2014112432 A1 WO2014112432 A1 WO 2014112432A1 JP 2014050290 W JP2014050290 W JP 2014050290W WO 2014112432 A1 WO2014112432 A1 WO 2014112432A1
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- WIPO (PCT)
- Prior art keywords
- slag
- converter
- dephosphorization
- hot metal
- desiliconization
- Prior art date
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Classifications
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- 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
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- 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
- C21C1/04—Removing impurities other than carbon, phosphorus or sulfur
-
- 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
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- 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
- C21C5/30—Regulating or controlling the blowing
- C21C5/35—Blowing from above and through the bath
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- 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
- C21C5/42—Constructional features of converters
- C21C5/46—Details or accessories
- C21C5/4606—Lances or injectors
- C21C5/4613—Refractory coated lances; Immersion lances
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- 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
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/40—Production or processing of lime, e.g. limestone regeneration of lime in pulp and sugar mills
Definitions
- the present invention relates to a converter steelmaking method, and in particular, proposes a method of steelmaking refining after performing desiliconization treatment and dephosphorization treatment of hot metal in combination with decarburization blowing in the converter.
- hot metal pretreatment for removing silicon and phosphorus in hot metal supplied from a blast furnace in advance of decarburization and refining by a converter.
- the hot metal pretreatment is performed in response to requests for cost reduction of refining flux, high purity of molten steel, improvement of manganese yield by preventing overoxidation in the converter, and reduction of refining slag amount.
- fluorine in the constituent components may be subject to legal regulations.
- a hot metal pretreatment method that does not use fluorite (CaF 2 ) as a fluorine source is effective.
- fluorite CaF 2
- a refining agent such as quick lime is added and at the same time a solid oxygen source such as gaseous oxygen or iron oxide is supplied, and silicon in the hot metal
- a converter type container that is, a converter. This is because it is advantageous to use a converter having a large furnace volume in order to use a large amount of scrap.
- Patent Document 1 desiliconization treatment is performed using a converter type reaction vessel, and after tapping and draining, the desiliconized hot metal is again charged into the converter type reaction vessel and dephosphorization is performed.
- a method of efficiently dephosphorizing without using fluorite is proposed by adjusting the silicon concentration in the hot metal after the desiliconization treatment, the basicity of the slag, and the iron oxide concentration.
- Patent Document 2 discloses that in a pretreatment method in which hot metal desiliconization and dephosphorization processes are continuously performed in a converter type vessel, 40 to 60% by mass of slag after precharge dephosphorization treatment is contained in the container. A method (double slag method) is disclosed in which the amount of slag generated is reduced by leaving it to be used for desiliconization and dephosphorization.
- Patent Document 3 in a method of refining hot metal using a converter that performs desiliconization treatment and dephosphorization treatment using a converter, intermediate desulfurization is performed after desiliconization treatment in the converter, and then dephosphorization is continued.
- a method of performing processing is disclosed. In this method, as will be described later, the dephosphorization after desiliconization is controlled through the control of the composition, and the subsequent dephosphorization treatment can be facilitated.
- Patent Document 2 desiliconization treatment and dephosphorization treatment are continuously performed in one converter-type vessel, and only 40 to 60% by mass of the slag is discharged after the dephosphorization treatment, and the rest is transferred to the next.
- a pretreatment method has been proposed to reduce the amount of solvent used and the amount of slag generated by using it for desiliconization and dephosphorization of charge, and reduction of heat loss can be expected.
- this document 2 does not describe an appropriate slag composition and a range of processing temperature in the desiliconization and dephosphorization processes, but also a dephosphorization process with a large amount of desiliconized slag remaining in the furnace.
- the main object of the present invention is to improve the efficiency of desiliconization and dephosphorization of hot metal with a small amount of a solvent, thereby reducing the cost of melting low phosphorous metal and reducing the cost of decarburization and refining. It is to propose a converter steelmaking method. Another object of the present invention is to provide an effective converter steelmaking method for expanding the effective utilization of slag generated during melting and reducing the loss of metal in the slag. It is in.
- the inventors can efficiently reduce the phosphorus concentration even when the amount of the solvent used is suppressed in the steelmaking refining process of desiliconization, dephosphorization, and decarburization.
- a method that can secure a heat source and improve iron yield was investigated.
- hot metal desiliconization treatment and hot metal dephosphorization treatment in the converter for hot metal pretreatment, decarburization and refining is performed at the time of either or both of desiliconization treatment and dephosphorization treatment.
- an upper blowing lance with a burner function having a combustion gas hole (burner hole) that can supply fuel gas and combustion-supporting gas simultaneously is used in addition to supplying oxygen gas and powder for refining.
- the present invention performs desiliconization treatment and dephosphorization treatment in conjunction with decarburization and refining of hot metal in the first converter, and then performs decarburization and refining in the second converter to obtain molten steel.
- the converter steelmaking method first, after the hot metal is charged into the first converter, the powder containing the smelting oxygen and the lime-based medium is sprayed from the lance to perform desiliconization of the hot metal, Next, after the desiliconization treatment, a part of the slag is discharged, and the remainder is treated with the intermediate waste to remain in the vessel together with the molten iron, and then after the desiliconization left in the converter Hot metal dephosphorization treatment is performed by spraying a powder containing oxygen for smelting and lime-based medium from the lance against the hot metal bath surface.
- the hot metal after dephosphorization is discharged and at least a part of the slag is left in the converter after the dephosphorization process, and then the hot metal after the dephosphorization process is transferred to the second converter.
- one or both of the above desiliconization treatment and the above dephosphorization treatment are carried out by using refining oxygen, powder containing lime-based medium, fuel gas, and combustion support. It is a converter steelmaking method characterized by using a lance with a burner function capable of blowing gas.
- the method of the present invention it is preferable to employ the following means.
- intermediate waste for discharging 40 mass% or more of the slag after the desiliconization treatment to the outside of the furnace is performed, and then the oxygen and lime for refining are used in the first converter using an upper blowing lance or a lance with a burner function.
- Dephosphorizing the hot metal by spraying the powder containing the system solvent material, or further fuel gas and supporting gas (2) Run with burner function during decarburization refining The use of, (3) At the time of the desiliconization treatment, the burner combustion heat amount supplied from the lance with a burner function used at the time of any one or more of the dephosphorization treatment and the decarburization refining is 10 MJ / t or more.
- the lance with burner function used for any one or more of desiliconization treatment, dephosphorization treatment, and decarburization refining includes a refining oxygen passage, a powder supply passage, a fuel gas passage, and a combustion-supporting gas.
- a multi-tube lance with a passage (5)
- the powder is blown with one or more of an iron oxide material and a manganese oxide together with a carrier gas composed of an inert gas such as argon or nitrogen, in addition to a solvent material and an auxiliary material, (6)
- the slag after the dephosphorization process leaves 60 mass% or more of the amount generated during the dephosphorization process in the converter.
- the lime content in the slag after dephosphorization can be used as a lime source in the desiliconization treatment of the next charge. Since it is possible to suppress dephosphorization in the silicon treatment, it is possible to reduce the amount of lime-based medium used in the steelmaking process, particularly in the entire hot metal pretreatment process.
- the intermediate waste is removed after the desiliconization process, and then the dephosphorization process is performed in the same converter.
- the slag after the high-temperature dephosphorization treatment generated by the precharge can be used as a solvent.
- the endothermic component can be utilized as heat for melting the cold iron source, and thus the amount of cold iron source (scrap) used can be increased, Metal loss can be reduced.
- a low basicity generated during desiliconization treatment by using an upper blowing acid lance with a burner function for combustion capable of blowing powder (hereinafter simply referred to as “lance with a burner function”).
- the slag can be easily discharged out of the furnace, and iron loss in the discharged slag can be reduced.
- the powder supplied from the burner hole of the lance with the burner function becomes a heat transfer medium, heat can be supplied to the hot metal and slag with high efficiency. Heat loss due to the addition of an iron oxide source used as a phosphorus agent can be compensated for, and at the same time, grain iron loss in the slag can be reduced.
- a pretreatment of hot metal and a decarburization refining are performed using a converter.
- a converter melting furnace 1 capable of top bottom blowing as shown in FIG. 1 is used.
- the lance 2 with the burner function which can be raised / lowered later explained in detail at the time of either one or both of desiliconization processing and dephosphorization processing with respect to the hot metal in the converter 1, that is, various This is characterized in that the oxygen gas for refining is blown toward the bath surface (molten metal) from the tip of the upper blowing acid lance 2 with a combustion burner function capable of blowing powder (up blowing).
- the bottom blowing is performed using a bottom blowing tuyere 3 provided at the bottom of the converter 1.
- oxygen gas or inert gas such as Ar gas or nitrogen gas is generally used, but by blowing into the hot metal, stirring of the hot metal is strengthened to promote melting of the cold iron source. Further, it may be a gas having a function to perform, or a gas having a function of blowing a solvent in the molten iron together with the carrier gas.
- symbol 4 in a figure is the tapping hole for tapping the hot metal 9 after refining.
- two or more converters are used, at least one of which is used for hot metal pretreatment, and at least one of the other converters is used for decarburization of pretreated hot metal.
- the pretreatment is performed in the first converter for hot metal pretreatment, and the hot metal after the pretreatment is transferred to the second converter for decarburization and refining. It is preferable.
- the lance 2 with a burner function which is characteristic in the present invention, is as shown in the sectional structure of FIG. As described above, this is an upper blowing acid lance with a combustion burner function capable of blowing powder.
- the lance 2 with a burner function has a concentric six-pipe structure, and the central passage uses an inert gas such as Ar or N 2 as a carrier gas, quick lime powder, iron oxide powder, Mn ore powder, and other solvent materials. 1 or two or more powdery refining materials (powder) for blowing powder, and a plurality of annular passages are provided outside the powder blowing passage 18.
- the annular passage is, in order from the inner side (inner pipe), a fuel gas passage 19, a combustion-supporting gas passage 20 such as combustion oxygen or air on the outer side, a refining oxygen gas passage 21 on the outer side, and A cooling water passage 22a, 22b having a structure in which the inner and outer passages are reversed and circulated at the lower end is arranged in the outermost outer portion of the outer portion.
- a lance tip 23 made of a copper casting is attached to the lower end of the main body of the lance 2 by welding or the like.
- the reason for adopting the lance 2 with a burner function capable of supplying the refining powder as described above in place of the normal top blowing acid lance is that the burner combustion heat is efficiently transferred to the molten metal. This is because the amount of heat necessary for scrap melting and the like can be effectively supplied.
- the refining powder injected from the lance serves as a heat transfer medium for burner combustion heat, and the refining powder itself is also added in a heated state, so that the slag temperature rises and the exhaust gas after the desiliconization process is increased.
- this lance 2 with a burner function when used in hot metal dephosphorization, since the dissolution of the lime source is promoted, the dephosphorization reaction is improved. Further, in decarburization blowing, using this lance 2 contributes to improving reaction efficiency such as promoting reduction of Mn ore.
- this hot metal preliminary treatment method is performed in the order of (A) hot metal charging, (B) desiliconization treatment, (C) intermediate waste removal, (D) dephosphorization treatment, and (E) tapping hot water.
- A hot metal charging
- B desiliconization treatment
- C intermediate waste removal
- D dephosphorization treatment
- E tapping hot water.
- Hot metal charging process (A) In this step (A), at least part of the dephosphorized slag (hereinafter simply referred to as “dephosphorized slag”) 17 generated during the previous hot metal preliminary treatment is transferred into the converter (smelting furnace) 1 in the furnace.
- the hot metal 9 is charged from the charging pan 14 while remaining in the hot pot, or after the cold iron source 11 such as iron scrap is charged before the hot metal charging, the hot metal 9 is charged.
- the cold iron source 11 charged in advance in the converter-type refining furnace 1 iron scrap such as directly reduced iron, cold iron, etc. as well as iron scrap stipulated in the “Iron Scrap Inspection Standard” of the Japan Iron Source Association The main component is used.
- the dephosphorization slag 17 generated during the previous refining (previous charge) to be left in the converter 1 for the next refining (next charge) has the role of adjusting the slag basicity during the desiliconization process of the next charge. That is, the basicity (mass% CaO / mass% SiO 2 ) (hereinafter simply referred to as “basicity”) of the dephosphorized slag is 1.2 or more, preferably 1.4 or more.
- the reason is that if the basicity of the dephosphorization slag 17 of the previous charge is less than 1.2, even if the dephosphorization slag remains, the basicity adjustment in the desiliconization treatment is insufficient, and a large amount of the lime-based solvent medium This is because it is necessary to add.
- the upper limit of the basicity is not particularly limited, but since the slag basicity in the normal hot metal dephosphorization treatment is about 3.0 or less, it is not particularly necessary to increase the basicity beyond this.
- the amount of the dephosphorization slag 17 of the previous charge remaining in the furnace is 30% by mass or more, preferably 60% by mass of the dephosphorization slag amount generated by the previous charge in order to effectively adjust the basicity. % To 100% by mass. If the entire amount of the dephosphorization slag 17 of the previous charge remaining in the furnace is utilized for the desiliconization process of the next charge, the basicity adjustment in the desiliconization process becomes easier. In addition, if such a method is continuously performed, the pretreated slag discharged is only desiliconized slag at the time of intermediate discharge, and dephosphorized slag with high basicity is not discharged. Problems such as expansion and alkali elution do not occur. Therefore, the method of the present invention is extremely effective in utilizing slag.
- the dephosphorization slag 17 has a relatively high basicity and a low temperature (about 1350 ° C. or less), and therefore has a high solid phase ratio and low fluidity. For this reason, inefficient operations such as adding a large amount of coolant and solidifying the decarburized slag in the furnace are not necessary in terms of heat balance and material balance. Further, since this dephosphorization slag 17 is rich in solid phase due to the above characteristics and has low fluidity, it contains a large amount of fine metallic iron in the structure. It contains about 6% by mass or more of metallic iron.
- slag at the end of desiliconization treatment slag after desiliconization treatment, hereinafter referred to as “desiliconization slag”
- desiliconization slag has a high liquid phase rate and relatively high fluidity, so that metallic iron in the slag is easily separated. There is little metal iron remaining in the slag without being recovered after the slag grinding and magnetic separation. Therefore, in the method of the present invention, iron loss into the slag can be reduced throughout the hot metal preliminary treatment.
- step (B) the converter 1 is erected and the refining oxygen gas 5 is injected mainly from the lance 2 with a burner function toward the molten iron 9 to perform desiliconization blowing, and also support combustion.
- This is a process for performing desiliconization by simultaneously spraying combustion oxygen, which is a reactive gas 6, fuel gas 7 and refining powder.
- the desiliconization process is characterized in that the powder for refining comprising the silicon source 15 and the lime-based solvent 16 contained in the hopper 8 is burned from the central passage 18 of the lance 2 with burner function into the combustion atmosphere by the burner. It is to spray on top. If necessary, these powders may be supplied from a chute not shown.
- the lance 2 with the burner function uses the burner function of the combustion-supporting gas 6 and the fuel gas 7 so that the carbon material serving as a heat source supplied from the central passage, the silicon source, the iron oxide serving as the oxygen source, and the like are similarly used. You may add to.
- oxygen source for desiliconization treatment from the viewpoint of dissolving a large amount of cold iron source 11, oxygen gas from the refining oxygen gas passage 21 of the lance 2 with burner function is used without using iron oxide having a large endothermic amount. Preferably only 5 is blown.
- silicon contained in the molten iron 9 or silicon contained in the silicon source 15 and the cold iron source 11 and transferred to the molten iron by dissolution reacts with the oxygen source (Si + O 2 ⁇ SiO 2 ).
- the reaction efficiency in the subsequent dephosphorization treatment can be increased. Oxidation heat is generated during the desiliconization process, and the hot metal temperature is increased by the oxidation heat, and the melting of the cold iron source 11 in the hot metal is promoted.
- the composition of the slag in this desiliconization treatment stage takes into account the amount of dephosphorization slag 17 of the previous charge previously left in the furnace, the estimated value of the composition, and the amount of silicon dioxide produced by the above reaction.
- the slag basicity at the end of the desiliconization process is adjusted to 0.5 or more and 1.5 or less. If the basicity is less than 0.5, the phosphorus removal from the previous charge dephosphorization slag 17 left in the furnace is reintroduced to increase the phosphorus concentration in the hot metal, and the dephosphorization load in the subsequent process is increased, which is efficient. Not.
- the basicity of the desiliconized slag at the end of the desiliconization treatment is 0.5 or more, more preferably 0.7 or more. Further, when the basicity is higher than 1.5, the fluidity of the slag is lowered, so that there is a problem that the amount of waste during the subsequent intermediate waste is reduced or the control of the amount of waste is difficult. It is not efficient in reducing the melting material. Therefore, the slag basicity at the end of the silicon removal treatment is 1.5 or less, more preferably 1.2 or less.
- steelmaking slag selected from decarburized slag, dephosphorized slag, ladle slag, and the like is used as a medium material in addition to lime-based medium materials such as quick lime, limestone, and dolomite.
- the hot metal temperature at the end of the desiliconization treatment is adjusted to 1260 ° C. or higher and 1450 ° C. or lower, more preferably 1400 ° C. or lower.
- the temperature is higher than 1450 ° C., the phosphorus is removed from the dephosphorization slag 17 left in the furnace and the concentration of phosphorus in the hot metal is increased.
- it is necessary to increase the concentration of magnesia in the slag in order to prevent the lining magnesia carbon bricks from being worn, resulting in high costs.
- control of the hot metal temperature at this stage is also effective for performing dephosphorization efficiently in the subsequent dephosphorization step.
- the hot metal temperature at the end of the desiliconization process is set to 1350 ° C. or less, the input amount of a coolant such as iron ore added for temperature adjustment in the dephosphorization process can be significantly reduced.
- a coolant such as iron ore added for temperature adjustment in the dephosphorization process
- the desiliconization process and the dephosphorization process are continuously performed in the same converter, it is difficult to charge the scrap before the dephosphorization process in terms of working time.
- cold iron sources such as scrap that can be thrown in from the furnace during processing are regular and expensive, or are limited in quantity such as bullion generated in the steelworks, so it is steady.
- the cold iron source may not be charged from the furnace due to the restriction on the number of types of secondary materials that can be used in the furnace charging apparatus.
- the coolant that has been conventionally used in the dephosphorization process is limited to iron oxide such as iron ore, and the fact is that cold iron sources such as inexpensive scrap cannot be fully utilized.
- the hot metal content is low, scraps may be left undissolved. However, it may be held in the converter as it is with the hot metal and melted until the next dephosphorization step. That is, for the cold iron source, there is no operational problem as long as the dissolution is completed by the end of the dephosphorization treatment.
- the hot metal temperature after the desiliconization treatment may be a value measured by a thermocouple or the like, or a value calculated from a heat balance may be used.
- the calculation method from the heat balance can be calculated based on the following equation (1), but is not necessarily limited to this. Although it tends to be slightly higher than a calculated value obtained by adjusting a coefficient according to individual apparatus conditions or operating conditions, or adding or deleting variables, it is an error level.
- T Hot metal temperature after desiliconization (° C)
- T i Hot metal temperature (° C)
- X p Hot metal unit (kg / t) (Same as below per 1 ton total of hot metal weight and cold iron source weight)
- X s Cold iron source unit (kg / t)
- X Si Silicon basic unit to be an oxide (kg / t)
- X C Carbon basic unit in additive (kg / t)
- X ore Iron oxide basic unit (kg / t)
- O2 Gaseous oxygen basic unit (Nm 3 / t)
- X f Solvent base unit (kg / t)
- W Converter molten iron capacity (t)
- X t Time (min) from the previous charge tapping until the desiliconization process is completed
- Silicon (X Si ), which is an oxide in the above formula (1), is the total amount contained in hot metal, cold iron source, additives, and the like.
- the silicon concentration in the hot metal a rapid analysis value of a sample collected from the hot metal before charging every charge is used.
- the silicon concentration in various cold iron sources for example, the analysis value of a representative sample for each lot is used, but cold iron is often stable at the same concentration as hot metal.
- the silicon concentration in scrap varies depending on the source, but on average it is stable at a concentration of about 1/10 or less of pig iron, so this may be used as a representative value or ignored. There is no problem.
- silicon that is not an oxide in the additive.
- This refers to iron silicide, metal silicon, silicon carbide, silicon nitride or other silicides.
- Typical additives include ferrosilicon and powder containing about 60% by weight of silicon carbide. The thing molded into briquettes (hereinafter referred to as silicon carbide briquettes) and the like can be mentioned.
- carbons in the additive there are other carbons in the additive.
- carbon source carbon in carbides such as silicon carbide as well as carbon materials such as coke or earthy graphite are used.
- auxiliary materials such as quick lime, light-burned dolomite, and magnesia clinker are used as the solvent in the additive.
- slag such as dephosphorized slag, decarburized slag, and ladle slag is also a source of calcium oxide.
- slag such as dephosphorized slag, decarburized slag, and ladle slag is also a source of calcium oxide.
- magnesium oxide can be used as a source of magnesium oxide.
- calcium or magnesium carbonates or hydroxides may be used, but these have a large endotherm, so when used in large quantities, distinguish them from other medium materials. It is desirable to modify the above equation (1).
- the hot metal temperature after this treatment is controlled to an appropriate range and silicon is used as a heat source, so that the total weight of the hot metal and the cold iron source is 100 to 300 kg / t. Even if a large amount of cold iron source is used, melting of the cold iron source and refining of the hot metal can be performed efficiently without causing a decrease in productivity and an increase in refining cost.
- the cold iron source basic unit is 300 kg / t or more, there is a problem that a further heat source is required, leading to an increase in cost, or a long blowing time and a decrease in productivity. Further, it is not efficient to further increase the amount of use due to restrictions on the charging equipment of the cold iron source.
- the slag after desiliconization treatment that is, to improve the exhaustability of the desiliconization slag 10
- Intensity of oxygen supplied to molten iron during desiliconization treatment is stoichiometrically in addition to the amount required for desiliconization 2 Nm 3 / t or more, preferably is preferably set to 4 Nm 3 / t or more.
- such an acid feeding is performed so that the silicon concentration in the hot metal at the end of the desiliconization treatment is 0.1 mass% or less, preferably 0.05 mass% or less. This makes it possible to maintain the forming state even when exhausting after the silicon removal treatment, to maintain good exhaustability, and to suppress dephosphorization from the slag to the molten iron.
- the acid feed rate from the lance 2 with a burner function is 1 to 3 Nm 3 / min ⁇ t
- the blowing rate of the bottom blowing gas is 0.1 to 0.6 Nm 3 / min ⁇ t. It has been confirmed that the above effects can be obtained.
- the exhaust gas concentration during desiliconization blowing, CO, CO 2 concentration in exhaust gas, exhaust gas flow rate, exhaust gas analysis value in order to perform slag discharge due to the progress of the decarburization reaction as described above. It is preferable to determine while monitoring the decarburization rate calculated from
- these steps (A) to (C) are repeatedly and continuously performed. Care must be taken because phosphoric acid accumulates in the furnace if the discharge of carbon is insufficient. If the amount of phosphoric acid in the furnace slag increases too much in the dephosphorization stage, the dephosphorization reaction efficiency decreases due to an increase in the phosphoric acid concentration in the slag, and the phosphorus concentration in the hot metal after the treatment increases, This is because there is a problem that the amount of lime-based medium necessary for the reaction increases.
- the lance 2 with a burner function is used.
- An example of suitable conditions for the desiliconization treatment of the present invention is shown in Table 1, and the effect is shown in FIG.
- Table 1 and FIG. 4 by using the lance 2 with a burner function, it is possible to effectively supply hot metal and slag, and by melting scrap, promoting lime and iron oxide melting, and promoting slag melting. It is possible to stabilize the intermediate rejection rate at a high level and reduce the granular iron in the intermediate rejection slag.
- the lance 2 with a burner function is used for the powder as these desiliconizing refining agent as in the present invention.
- the slag is more efficiently melted because the blown powder such as a refining flux to be added is heated before reaching the bath surface. That is, as shown in FIG. 4, when paying attention to the intermediate waste, when the heat supply of 10 MJ / t or more is performed by the lance 2 with a burner function, the desiliconization slag waste rate is dramatically improved.
- the ratio of the granular iron suspended in the slag was observed, it was 10% by mass in the case of using a normal blower lance without a burner, but with a burner function in which the amount of heat generated by combustion of the burner is 10 MJ / t or more.
- the lance 2 was used, it was reduced to 6% by mass.
- the basicity of the slag at the end of the desiliconization treatment is in the range of 0.5 to 1.5, and the hot metal temperature at the end of the desiliconization treatment process is 1260 ° C. or higher and 1350 ° C. or lower.
- slag forming is promoted by optimizing oxygen intensity.
- the amount of slag when adjusting the tilt angle of the furnace body so that hot metal does not flow out, the amount of slag must be left in the furnace, but the forming slag has a true specific gravity. Since the bulk specific gravity is reduced, the amount of slag remaining in the furnace can be controlled to be low.
- the hot metal remaining in the same converter 1 is supplied with a powder containing a lime-based medium solvent as a dephosphorizing refining agent and an oxygen source to remove the hot metal.
- Phosphorus treatment As the oxygen source used in this dephosphorization process, it is preferable to use only the oxygen gas 5 from the upper blowing lance 2 with a burner function in order to reduce heat loss. Phosphorus in the hot metal is oxidized by oxygen in the supplied oxygen source to become phosphor oxide (P 2 O 5 ), and this phosphor oxide is stably taken into the slag generated by the incubation of the lime-based solvent.
- the hot metal dephosphorization proceeds.
- the lance 2 or chute with burner function is used so that the basicity of the slag after dephosphorization (the dephosphorization slag 17 of the current charge) is 1.2 or more and 3.0 or less. It is preferable to perform the dephosphorization treatment by spraying or charging the lime-based medium solution using slag and the hot metal temperature after the completion of the dephosphorization treatment by acid feeding to be 1280 ° C. or higher and 1360 ° C. or lower.
- the reason for this is that when the slag basicity of the dephosphorization slag 17 of the current charge produced during the dephosphorization process is less than 1.2 or the hot metal temperature is higher than 1360 ° C., the dephosphorization ability of the slag decreases, In some cases, the phosphorus concentration in the hot metal cannot be lowered sufficiently.
- the slag basicity exceeds 3.0, it becomes difficult to hatch the lime-based medium solvent, the cost of the lime-based medium solvent increases, and even when the hot metal temperature is less than 1280 ° C., the lime-based medium solvent is also hatched. The amount of heat at the time of decarburization and refining in the subsequent process is insufficient.
- finish of a dephosphorization process shall be 1280 degreeC or more and 1360 degrees C or less, and the hot metal at the time of the completion
- this dephosphorization step (D) the effect of applying the lance 2 with a burner function is as shown in FIG. That is, in the lance 2 with the burner function, the dephosphorizing powder such as lime and iron oxide becomes a heat transfer medium for the burner combustion heat, and at the same time, the dephosphorizing agent itself is heated to promote the mass transfer of the dephosphorizing component. As a result, the dephosphorization efficiency is increased. As shown in FIG. 5, when heat is supplied through the lance 2 with the burner function as the burner combustion heat amount through the lance 2 with the burner function, [P] after processing is low stable. Can be understood.
- Hot spring process (E) In this step (E), when the phosphorus concentration in the hot metal is lowered to a predetermined value through the dephosphorization step (D), the converter 1 is tilted to the side where the tap is installed, The hot metal in the converter-type refining furnace is poured out into a hot metal holding container (not shown).
- the dephosphorized hot metal discharged from the hot water is then decarburized as a second converter.
- a predetermined molten steel is refined by decarburization refining using a refining converter, that is, a top-bottom blowing converter.
- decarburization treatment is performed using the dephosphorized hot metal, it is not necessary to lower the end point carbon concentration and to improve the dephosphorization by promoting the formation of FeO in the end point slag. It is advantageous. However, in order to reduce Mn ore, it is necessary to compensate for heat of reduction and improve the efficiency of reducing Mn ore.
- the use of the lance 2 with a burner function under the conditions shown in Table 3 is effective as shown in FIG. That is, as shown in FIG. 6, when Mn ore reduction is performed in a decarburizing and refining converter, the heat supply amount from the burner is 10 MJ / t or more mainly using Mn ore with the burner function lance 2 or chute.
- the heat supply amount from the burner is 10 MJ / t or more mainly using Mn ore with the burner function lance 2 or chute.
- the present invention uses an upper blowing lance with a burner function, which can improve the rejection rate after desiliconization and reduce the granular iron in the slag. It becomes.
- a hot metal preliminary treatment was performed using a converter 1 having a capacity of 300 tons as shown in FIG.
- refining oxygen gas is blown toward the bath surface (hot metal) using the lance 2 with a burner function shown in FIG. 3, and hot metal is being melted from the eight bottom blowing tuyeres provided at the bottom of the furnace body.
- Nitrogen gas for stirring was blown into the container.
- a quadruple lance without the fuel gas passage 19 and the combustion-supporting gas passage was used in FIG.
- the conditions of desiliconization blowing, dephosphorization blowing, and decarburization refining in the decarburization converter are shown in Tables 1 to 3, but the hot metal components are listed in Table 4.
- the basicity compensation of the slag produced in the desiliconization treatment was performed by adding lump lime as an input chute or powdery lime from the powder blowing passage 18 of the lance 2 with a burner function under burner combustion. Further, the end of the desiliconization blowing (treatment) in the hot metal preliminary treatment stage was determined by changes in the exhaust gas temperature and the CO concentration in the exhaust gas. The intermediate rejection rate in the table was evaluated by weighing the slag pan.
- This example shows the result of investigating the influence of the dephosphorization slag residual rate during desiliconization blowing.
- the converter and burner used were the same as those in Example 1, and the blowing conditions were basically the same as those in Example 1.
- the dephosphorization slag residual ratio was Only the operating conditions were changed. The results are shown in Tables 5-1 to 5-3.
- the present invention is a technique related to a steelmaking method for a converter, but is naturally effective as a so-called hot metal pretreatment technique.
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Abstract
Description
また、本発明の他の目的は、溶製時に発生するスラグの有効利用を拡大できるようにすること、およびスラグ中への地金ロスを低減するために有効な転炉製鋼法を提案することにある。
次に、脱燐後の溶銑を出湯すると共に、脱燐処理後スラグの少なくとも一部を転炉内に残留させ、その後、出湯した脱燐処理後の溶銑を上記第2の転炉に移して脱炭精錬を行なって溶鋼を得る際に、上記脱珪処理および上記脱燐処理のいずれか一方もしくは両方の処理を、精錬用酸素、石灰系媒溶材を含む粉体、燃料ガスおよび支燃性ガスを吹き付けることのできるバーナー機能付きランスを用いて行なうことを特徴とする転炉製鋼法である。
(1)前記第1の転炉内に、前回脱燐処理時に生成した量の30mass%以上の脱燐処理後スラグを残留させ、さらにその第1の転炉内には、少なくとも未処理の溶銑を装入すると共に、上吹きランスもしくはバーナー機能付きランスから精錬用酸素および石灰系媒溶材を含む粉体、もしくはさらに燃料ガスおよび支燃性ガスを吹き付けることによって溶銑の脱珪処理を行ない、次に、脱珪処理後のスラグの40mass%以上を炉外に排出する中間排滓を行ない、その後、上記第1の転炉にて上吹きランスもしくはバーナー機能付きランスを用いて精錬用酸素および石灰系媒溶材を含む粉体、もしくはさらに燃料ガスおよび支燃性ガスを吹き付けることによって溶銑の脱燐処理を行なうこと
(2)脱炭精錬時に前記バーナー機能付きランスを用いること、
(3)前記脱珪処理時、前記脱燐処理、前記脱炭精錬のいずれか1または2以上の処理時に用いる前記バーナー機能付きランスから供給するバーナー燃焼熱量は、10MJ/t以上とすること、
(4)脱珪処理、脱燐処理、脱炭精錬のいずれか1または2以上の処理に用いる前記バーナー機能付きランスは、精錬用酸素通路および粉体供給通路、燃料ガス通路、支燃性ガス通路を有する多重管ランスであること、
(5)前記粉体は、媒溶材や副原料の他、酸化鉄材料やマンガン酸化物のいずれか1以上を、アルゴンや窒素の如き不活性ガスからなる搬送ガスと共に吹き込むこと、
(6)脱燐処理後スラグは、脱燐処理時に生成した量の60mass%以上を転炉内に残留させること、
(2)本発明によれば、溶銑予備処理工程において、脱珪処理後に中間排滓し、引き続き同じ転炉で脱燐処理を行なうので、精錬容器の移し替えによる放熱相当分を冷鉄源溶解のための熱源とすることができると共に、前チャージで生成した高温の脱燐処理後スラグを媒溶材として活用できる。従って、常温の媒溶材を添加する場合に比較すると、吸熱分を冷鉄源溶解のための熱として活用することができ、ひいては冷鉄源(スクラップ)使用量の増大を図ることができる他、地金ロスを低減することができる。
(3)本発明によれば、溶銑予備処理工程において、脱珪処理と脱燐処理との間で、脱珪処理時に生成した低塩基度のスラグを炉外に排出するため、比較的高い塩基度((質量%CaO/質量%SiO2)=1.2~3.0)を維持でき、従って、脱燐処理における石灰系媒溶材の使用量を低減させることができる。
(4)本発明によれば、粉体吹き込み可能な燃焼用バーナー機能付き上吹き送酸ランス(以下、単に「バーナー機能付きランス」という)を用いることで、脱珪処理時に生成した低塩基度のスラグを炉外に排出しやすくなると共に、排出スラグ中の鉄ロスを低減することができる。
(5)本発明によれば、前記バーナー機能付きランスのバーナー孔から供給される粉体が伝熱媒体となり、高い効率で溶銑、スラグへの熱供給が可能になるため、スクラップの溶解、脱燐剤として使用する酸化鉄源添加による熱ロスを補なうことができると同時に、スラグ中の粒鉄ロスも低減させることができる。
(6)本発明によれば、前記バーナー機能付きランスのバーナー孔から供給される粉体が伝熱媒体となる際に、この粉体が加熱されるため、溶銑の脱燐吹錬におけるフラックスによる脱燐効率の向上、脱炭精錬時におけるMn鉱石の還元促進に寄与し、精錬コストの低減を図ることができる。
この工程(A)では、転炉(精錬炉)1内に、前回の溶銑の予備処理時に生成した脱燐処理後スラグ(以下、単に「脱燐スラグ」という)17の少なくとも一部を炉内に残留させたまま、装入鍋14より新たな溶銑9を装入するか、または、その溶銑装入前に鉄スクラップなどの冷鉄源11を装入した後に該溶銑9を装入する。転炉型精錬炉1内に予め装入する冷鉄源11としては、日本鉄源協会の「鉄スクラップ検収統一規格」に規定されている鉄スクラップの他、直接還元鉄、冷銑などの鉄を主成分とするものを用いる。
この工程(B)は、転炉1を直立させ、前記バーナー機能付きランス2等から主に溶銑9に向けて精錬用酸素ガス5を噴射して脱珪吹錬を行ないつつ、併せて支燃性ガス6である燃焼用酸素と燃料ガス7と精錬用粉体とを同時に吹き付けて脱珪を行なう処理である。特に、この脱珪処理工程の特徴は、ホッパー8内に収容された珪素源15および石灰系媒溶材16からなる精錬用粉体を前記バーナー機能付きランス2の中心通路18からバーナーによる燃焼雰囲気中で上吹き噴射することにある。なお、必要に応じ、図示していないシュートからこれらの粉体を供給してもよい。このとき、該バーナー機能付きランス2は、支燃性ガス6と燃料ガス7とによるバーナー機能により、中心通路から供給される熱源となる炭材や珪素源あるいは酸素源となる酸化鉄などを同様に添加してもよい。脱珪処理のための酸素源としては、多量の冷鉄源11を溶解させる観点からは、吸熱量の大きい酸化鉄を用いずに該バーナー機能付きランス2の精錬用酸素ガス通路21から酸素ガス5のみを吹き込むことが好ましい。
T:脱珪処理後溶銑温度(℃)
Ti:装入溶銑温度(℃)
Xp:溶銑原単位(kg/t)(溶銑重量と冷鉄源重量の合計1t当たり、以下同様)
Xs:冷鉄源原単位(kg/t)
XSi:酸化物となる珪素原単位(kg/t)
XC:添加物中炭素原単位(kg/t)
Xore:酸化鉄原単位(kg/t)
XO2:気体酸素原単位(Nm3/t)
Xf:媒溶材原単位(kg/t)
W:転炉溶鉄容量(t)
Xt:前チャージ出銑から脱珪処理終了までの時間(分)
本発明において、溶銑の予備処理に当たっては、前述した脱珪処理後にその脱珪スラグの排滓する工程を設ける。この排滓工程(C)において、脱珪処理時に発生した大量のSiO2を含む低塩基度の脱珪スラグが該転炉1から排出される。所謂、脱珪スラグ10を排出することは、次工程の脱燐処理において、適切なスラグ塩基度が得られるようにするため、および石灰系媒溶材の使用量を低減するために有効である。また、前回チャージの脱燐スラグ17を大量に炉内に残留させたまま次回チャージで新たな溶銑の脱珪処理を行なう溶銑の予備処理方法の場合、スラグから溶銑への復燐を防止するように脱珪処理するため、脱珪スラグ中の燐酸濃度が従来よりも高くなる。従って、もし該脱珪スラグを転炉1内に大量に残留させた場合、次の脱燐処理工程における炉内スラグ中の燐酸量が過大になって脱燐効果が低下することから、これを防止する上でもこの工程(C)の役割は重要である。なお、脱珪吹錬終了後の中間排滓は、転炉を傾動させ、炉口から排出しても、溶銑の出湯孔4から行なってもよい。
前記排滓工程(C)の後は、同じ一の転炉1内に残留させた溶銑に脱燐用精錬剤である石灰系媒溶剤を含む粉体および酸素源を供給して、溶銑を脱燐処理する。この脱燐処理工程において使用する酸素源は、前記バーナー機能付き上吹きランス2からの酸素ガス5のみを使用することが熱ロスを低減するうえで好ましい。溶銑中の燐は、供給される酸素源中の酸素により酸化されて燐酸化物(P2O5)となり、この燐酸化物が、石灰系媒溶剤の滓化によって生成するスラグ中に安定的に取り込まれて、溶銑の脱燐が進行する。脱燐反応を効率よく進めるには、脱燐処理後のスラグ(今回チャージの脱燐スラグ17)の塩基度は1.2以上3.0以下となるように、前記バーナー機能付きランス2もしくはシュートを使って前記石灰系媒溶材を吹き付けもしくは投入し、かつ送酸によって脱燐処理終了後の溶銑温度が1280℃以上1360℃以下となるようにして脱燐処理を行なうことが好ましい。
この工程(E)では、前記の脱燐工程(D)を経て溶銑中の燐濃度が所定の値にまで低下したとき、該転炉1を出湯口が設置された側に傾転させて、転炉型精錬炉内の溶銑を溶銑保持容器(図示せず)に出湯する。
前記工程(A)~(E)からなる第1の転炉1による溶銑予備処理を経て、出湯された脱燐溶銑は、次に、第2の転炉である脱炭精錬用転炉、即ち、上底吹き転炉を用いて脱炭精錬して所定の溶鋼を精製する。この工程では、脱燐された溶銑を用いて脱炭処理するため、終点炭素濃度を低くし、終点スラグ中のFeO生成促進により脱燐の向上を図る必要がないため、例えば、Mn鉱石還元に有利である。しかしながら、Mn鉱石還元のためには還元熱の補償、Mn鉱石還元効率向上が必要である。この点、前記バーナー機能付きランス2を表3に示す条件で使用すると、図6に示すとおり有効である。即ち、図6に示すように、脱炭精錬用転炉において、Mn鉱石還元を行なう場合、主にMn鉱石該バーナー機能付きランス2もしくはシュートを使って、バーナーからの熱供給量10MJ/t以上になるように吹き付けもしくは投入することにより、Mn鉱石還元時の熱補償が可能となると同時に、還元効率も向上し、Mn歩留まりの向上に寄与する。
2 バーナー機能付き上吹きランス
3 底吹き羽口
4 出湯口
5 精錬用酸素ガス
6 支燃性ガス
7 燃料ガス
8 ホッパー
9 溶銑
10 脱珪スラグ
11 冷鉄源
14 装入鍋
17 脱燐スラグ
18 粉体吹き込み通路
19 燃料ガス通路
20 支燃性ガス通路
21 精錬用酸素ガス通路
22a 冷却水通路
22b 冷却水通路
Claims (7)
- 第1の転炉にて溶銑の脱炭精錬に併せて脱珪処理および脱燐処理を行ない、次に、第2の転炉にて脱炭精錬を行なって溶鋼とする転炉製鋼法において、
まず、前記第1の転炉内に溶銑を装入したのち、ランスから精錬用酸素および石灰系媒溶材を含む粉体を吹き付けることによって、溶銑の脱珪処理を行ない、
次に、その脱珪処理後スラグの一部を排滓して、その残りは溶銑と共に該容器内に残留させる中間排滓の処理を行ない、
次に、該転炉内に残した脱珪後の溶銑の浴面に対し、ランスから精錬用酸素および石灰系媒溶材を含む粉体を吹き付けることによって溶銑の脱燐処理を行ない、
次に、脱燐後の溶銑を出湯すると共に、脱燐処理後スラグの少なくとも一部を転炉内に残留させ、
その後、出湯した脱燐処理後の溶銑を上記第2の転炉に移して脱炭精錬を行なって溶鋼を得る際に、
上記脱珪処理および上記脱燐処理のいずれか一方もしくは両方の処理を、精錬用酸素、石灰系媒溶材を含む粉体、燃料ガスおよび支燃性ガスを吹き付けることのできるバーナー機能付きランスを用いて行なうことを特徴とする転炉製鋼法。 - 前記第1の転炉内に、前回脱燐処理時に生成した量の30mass%以上の脱燐処理後スラグを残留させ、さらにその第1の転炉内には、少なくとも未処理の溶銑を装入すると共に、上吹きランスもしくはバーナー機能付きランスから精錬用酸素および石灰系媒溶材を含む粉体、もしくはさらに燃料ガスおよび支燃性ガスを吹き付けることによって溶銑の脱珪処理を行ない、
次に、脱珪処理後のスラグの40mass%以上を炉外に排出する中間排滓を行ない、
その後、上記第1の転炉にて上吹きランスもしくはバーナー機能付きランスを用いて精錬用酸素および石灰系媒溶材を含む粉体、もしくはさらに燃料ガスおよび支燃性ガスを吹き付けることによって溶銑の脱燐処理を行なうこと、を特徴とする請求項1に記載の転炉製鋼法。 - 脱炭精錬時に前記バーナー機能付きランスを用いることを特徴とする請求項1または2に記載の転炉製鋼法。
- 前記脱珪処理時、前記脱燐処理、前記脱炭精錬のいずれか1または2以上の処理時における前記バーナー機能付きランスから供給するバーナー燃焼熱量は、10MJ/t以上にすることを特徴とする請求項1~3のいずれか1に記載の転炉製鋼法。
- 脱珪処理、脱燐処理、脱炭精錬のいずれか1または2以上の処理に用いる前記バーナー機能付きランスは、精錬用酸素通路および粉体供給通路、燃料ガス通路、支燃性ガス通路を有する多重管ランスであることを特徴とする請求項1~4のいずれか1に記載の転炉製鋼法。
- 前記粉体は、媒溶材や副原料の他、酸化鉄材料やマンガン酸化物のいずれか1以上を、アルゴンや窒素の如き不活性ガスからなる搬送ガスと共に吹き込むことを特徴とする請求項1~5のいずれか1に記載の転炉製鋼法。
- 脱燐処理後スラグは、脱燐処理時に生成した量の60mass%以上を転炉内に残留させることを特徴とする請求項1~6のいずれか1に記載の転炉製鋼法。
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TWI550092B (zh) | 2016-09-21 |
BR112015016963B1 (pt) | 2019-07-16 |
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