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WO2016098347A1 - Procédé de prétraitement de fer fondu - Google Patents

Procédé de prétraitement de fer fondu Download PDF

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Publication number
WO2016098347A1
WO2016098347A1 PCT/JP2015/006258 JP2015006258W WO2016098347A1 WO 2016098347 A1 WO2016098347 A1 WO 2016098347A1 JP 2015006258 W JP2015006258 W JP 2015006258W WO 2016098347 A1 WO2016098347 A1 WO 2016098347A1
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WIPO (PCT)
Prior art keywords
slag
dephosphorization
hot metal
furnace
desiliconization
Prior art date
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Ceased
Application number
PCT/JP2015/006258
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English (en)
Japanese (ja)
Inventor
孝彦 前田
川畑　涼
田中　高太郎
和人 百崎
俊朗 石毛
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JFE Steel Corp
Original Assignee
JFE Steel Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Application filed by JFE Steel Corp filed Critical JFE Steel Corp
Priority to CN201580068170.6A priority Critical patent/CN107002154A/zh
Priority to CN202210608276.2A priority patent/CN115074489A/zh
Priority to JP2016506016A priority patent/JP5983900B1/ja
Priority to KR1020177015093A priority patent/KR101896429B1/ko
Publication of WO2016098347A1 publication Critical patent/WO2016098347A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • 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
    • C21C1/04—Removing impurities other than carbon, phosphorus or sulfur
    • 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 pretreatment method using a converter-type refining furnace, and more specifically, using one converter refining furnace, the hot metal discharged from a blast furnace is efficiently processed.
  • the present invention relates to a pretreatment method for desiliconization and dephosphorization.
  • the dephosphorization treatment allows the produced phosphorous oxide (P 2 O 5 ) to be absorbed by CaO-based slag to advance the dephosphorylation reaction.
  • the desiliconization reaction is first performed. Occurring and dephosphorization occurs after the amount of silicon in the hot metal is reduced. Since silicon becomes SiO 2 (silicon dioxide) when oxidized, the amount of SiO 2 generated in the dephosphorization process increases when the silicon concentration in the hot metal before the dephosphorization process is high.
  • Patent Document 1 when performing desiliconization and dephosphorization of hot metal using one converter-type refining furnace, the dephosphorization slag generated by the previous charge (previous heat) is discharged ( Instead of slag (discharging), the hot metal from the next charge (heat) is charged into the converter smelting furnace. Then, desiliconization treatment is performed on the hot metal, and at the time when the silicon concentration in the hot metal becomes 0.2 mass% or less, at least a part of the in-furnace slag having a basicity in the range of 1.0 to 3.0 is obtained.
  • a preliminary treatment method has been proposed in which the dephosphorization process is performed, followed by dephosphorization.
  • dephosphorization slag is slag produced by dephosphorization treatment.
  • Charge (heat) is a concept in which the unit from the introduction of new hot metal to the completion of refining in that furnace and the discharge of hot metal or molten steel from the furnace is one unit. A single charge includes multiple refining operations that are held inside and interrupted.
  • Patent Document 2 when performing desiliconization treatment and dephosphorization treatment using one converter-type refining furnace, the hot metal of the next charge is discharged without removing the dephosphorization slag generated by the previous charge. It is charged in a converter-type refining furnace, and this silicon metal is desiliconized. Then, the silicon concentration of the hot metal at the end of the desiliconization treatment is 0.2 mass% or less, the slag basicity after the desiliconization treatment is 0.5 to 1.5, and the hot metal temperature after the desiliconization treatment is 1240 to 1400 ° C. Then, a preliminary treatment method has been proposed in which 40 mass% or more of the slag after the desiliconization treatment is discharged and then dephosphorization refining is performed on the molten iron in the furnace.
  • Patent Document 1 By applying the technology proposed in Patent Document 1 or Patent Document 2 and used for adjusting the basicity of slag in the desiliconization process of the next charge without eliminating the dephosphorization slag generated in the previous charge.
  • the technique proposed by patent document 2 while reducing the slag basicity after a desiliconization process, hot metal temperature is reduced.
  • “recovered phosphorus” is a phenomenon in which the phosphorus oxide (P 2 O 5 ) contained in the slag is decomposed, phosphorus is transferred to hot metal, and the phosphorus concentration of the hot metal is increased.
  • the dephosphorization slag generated by the dephosphorization process is used for the desiliconization process of the next charge, and the slag in the furnace is discharged during the desiliconization process and the dephosphorization process (""Intermediate slag discharging" is essential.
  • the dephosphorization slag is low in basicity, if the dephosphorization slag is used in the desiliconization process of the next charge, the SiO 2 generated during the desiliconization process causes the SiO 2 and the denitration remaining in the furnace to remain. The basicity of desiliconized slag produced with phosphorus slag is further reduced.
  • desiliconization slag is slag generated by the desiliconization process.
  • the basicity may be unexpectedly decreased or the amount of slag may be increased. If the dephosphorization slag generated by such dephosphorization process is used for the desiliconization process of the next charge without being discharged, slag will be ejected from the furnace port during the refining process, and the refining process may be interrupted. As a result, the problem that the productivity of the preliminary process decreases, that is, the ratio of the preliminary process decreases, also occurs.
  • the dephosphorization slag from the previous charge may be used in the desiliconization process of the next charge without being rejected, thereby obstructing the operation.
  • Patent Document 1 and Patent Document 2 do not give any consideration to these problems.
  • the present invention has been made in view of the above circumstances.
  • the object of the present invention is to perform desiliconization treatment and dephosphorization treatment of hot metal discharged from a blast furnace using one converter-type refining furnace.
  • the hot metal pretreatment method which is performed in succession sequentially, the mass and composition status of the slag remaining in the furnace during the hot metal pretreatment operation continuously performed over multiple charges Even if it is difficult to do so, the hot metal is subjected to an optimal pretreatment method according to the situation, and the amount of new CaO-based solvent other than slag to be reused and the amount of slag discharged are suppressed.
  • Another object of the present invention is to provide a hot metal pretreatment method capable of efficiently performing desiliconization and dephosphorization.
  • the gist of the present invention for solving the above problems is as follows.
  • [1] Using one converter-type refining furnace, the desiliconization process for desiliconizing the molten iron discharged from the blast furnace, and the desiliconizing process with the desiliconized molten iron remaining in the refining furnace An intermediate waste process for discharging at least a part of the desiliconized slag generated in the silicon treatment process from the refining furnace, and a dephosphorization process for dephosphorizing the molten iron remaining in the refining furnace in the intermediate waste process
  • the hot metal was pretreated by performing a phosphorous treatment step and a hot water step of tapping the hot metal treated with dephosphorization from the smelting furnace in this order, the hot metal was produced in the dephosphorization step after the hot water step.
  • Whether or not to discharge the dephosphorization slag in the refining furnace to the outside of the furnace is determined based on the phosphorus content analysis value of the hot metal after the dephosphorization treatment of the charge, and when it is determined to discharge the dephosphorization slag Decided to discharge dephosphorization slag from the smelting furnace and not dephosphorization slag. Without discharging the dephosphorization slag from the smelting furnace when, then, charged with molten iron of the next charge into the smelting furnace, and performing the preliminary treatment, hot metal pretreatment methods.
  • the dephosphorization slag is purified [1], wherein the dephosphorization slag is discharged from the refining furnace when the phosphorus content analysis value of the hot metal after the dephosphorization treatment exceeds the predetermined value Z without being discharged from the furnace.
  • the hot metal pretreatment method according to claim 1.
  • the hot metal reserve according to any one of [1] to [3] above, wherein the silicon content of the hot metal before the desiliconization treatment step is 0.70% by mass or less. Processing method.
  • the hot metal preliminary treatment method in which the desiliconization treatment and the dephosphorization treatment of the hot metal discharged from the blast furnace are continuously performed using one converter-type refining furnace, It is determined whether or not the dephosphorization slag in the furnace is discharged outside the furnace based on the analysis value of the phosphorus content of the hot metal during the hot metal pretreatment operation continuously performed over a plurality of charges. Even if it is difficult to accurately grasp the mass and composition of the slag remaining in the furnace, the hot metal is subjected to an optimal pretreatment method according to the situation. The amount of the CaO-based solvent used is suppressed, and the hot metal is efficiently desiliconized and efficiently dephosphorized.
  • FIG. 1 It is a schematic longitudinal cross-sectional view of the converter type refining furnace used when implementing the hot metal pre-processing method concerning this invention. It is the schematic which shows the hot metal pre-processing method of the said charge when the hot metal pre-processing method which concerns on this invention is applied to 2 continuous charge, and the dephosphorization slag of a pre-charge is not discharged
  • FIG. 1 is a schematic longitudinal sectional view of a converter-type refining furnace used when carrying out the hot metal pretreatment method according to the present invention.
  • FIG. 2 shows the hot metal pretreatment method of the present invention in the order of steps when the hot metal pretreatment method according to the present invention is applied to two consecutive charges and the pre-charge dephosphorization slag is not discharged out of the furnace.
  • FIG. FIG. 1 is a diagram showing the desiliconization process of FIG. 2- (B).
  • a converter-type refining furnace 1 capable of top-and-bottom blowing as shown in FIG. 1 is used.
  • the top blowing is performed by supplying an oxygen-containing gas as an oxygen source toward the hot metal 5 from the tip of the top blowing lance 2 via the top blowing lance 2 that can move up and down inside the converter type refining furnace 1.
  • oxygen-containing gas oxygen gas, oxygen-enriched air, air, or a mixed gas of oxygen gas and inert gas can be used.
  • FIG. 1 shows an example in which oxygen gas 9 is used as the oxygen-containing gas.
  • the oxygen gas 9 is industrial pure oxygen.
  • the bottom blowing is performed through a bottom-blowing tuyere 3 provided at the bottom of the converter-type refining furnace 1.
  • the bottom blowing gas 10 may be a gas containing oxygen gas or only an inert gas such as argon gas or nitrogen gas.
  • the bottom blowing gas 10 has a function of enhancing the stirring of the hot metal 5 by blowing it into the hot metal and promoting the melting of the cold iron source, as well as a slag forming agent along with the conveying gas from the bottom blowing tuyere 3. ) May be blown into the hot metal.
  • two or more converter-type refining furnaces 1 are used for refining the hot metal 5.
  • At least one converter-type smelting furnace 1 is used for the hot metal preliminary treatment according to the present invention, and the remaining at least one converter-type smelting furnace 1 is used as a pure oxygen converter for steelmaking for decarburization and refining.
  • decarburization refining (converter steelmaking) of the hot metal 5 subjected to the hot metal pretreatment according to the present invention is performed. That is, the pretreatment is performed in the converter type refining furnace 1 for hot metal pretreatment, and then the hot metal 5 subjected to the pretreatment is transferred to a pure oxygen converter for steelmaking for decarburization and decarburization and refining.
  • the present invention is applied to the case where two or more charges are continuously pretreated using one converter-type refining furnace 1, and preferably, 10 or more charges are continuously pretreated. Applies to cases.
  • the desiliconization process and the dephosphorization process are performed on the hot metal 5 using one converter-type refining furnace 1, and in this case, the refining pattern is the refining pattern 1 or the refining pattern 2.
  • the pretreatment is performed with one refining pattern selected from the following two types of refining patterns.
  • Refining pattern 1 a desiliconization process for desiliconizing hot metal in a converter type refining furnace, an intermediate waste process for discharging desiliconized slag generated in the desiliconization process from the converter type refining furnace, A dephosphorization process for dephosphorizing the hot metal remaining in the converter type refining furnace, a hot water process for removing the dephosphorized hot metal from the converter type refining furnace, and a dephosphorization process.
  • a refining method in which a hot metal charging step of charging molten iron of the next charge into the converter refining furnace without discharging the dephosphorized slag from the converter refining furnace in this order.
  • Refining pattern 2 Desiliconization process for desiliconizing the hot metal in the converter type refining furnace, and intermediate waste process for discharging the desiliconized slag generated in the desiliconization process from the converter type refining furnace, A dephosphorization process for dephosphorizing the hot metal remaining in the converter type refining furnace, a hot water process for removing the dephosphorized hot metal from the converter type refining furnace, and a dephosphorization process.
  • a refining method in which a dephosphorization process for discharging the dephosphorized slag from the converter type refining furnace and a hot metal charging process for charging the molten iron of the next charge into the converter type refining furnace in this order.
  • the refining pattern 1 will be described in the order of each process.
  • the total amount of the dephosphorization slag 7 generated in the pre-charge dephosphorization process Remains in the furnace.
  • a cold iron source 8 such as iron scrap is charged on the dephosphorization slag 7 remaining in the converter-type refining furnace 1, and the hot metal 5 used for the charge discharged from the blast furnace is charged into a charging pot (charging). ladle) 11 (welding process).
  • the hot metal 5 is charged into the empty converter-type refining furnace 1 after charging the cold iron source 8 such as iron scrap.
  • oxygen gas and / or iron oxide is supplied as an oxygen source to the hot metal 5 in the converter type refining furnace, and desiliconization treatment is performed as shown in FIG. Process).
  • Silicon contained in the molten iron 5 reacts with oxygen in the oxygen source to be supplied (desiliconization reaction; Si + 2O ⁇ SiO 2 ), and desiliconization proceeds.
  • the hot metal temperature rises due to the oxidation heat of silicon by this desiliconization reaction, and the dissolution of the cold iron source 8 in the hot metal is promoted.
  • the pre-charge dephosphorization slag 7 remaining in the furnace is mixed and reacted with the SiO 2 produced by the desiliconization reaction and the iron oxide produced by the reaction with the supplied oxygen source and the added iron making agent, Desiliconized slag 6 is generated in the furnace.
  • the hot metal after the desiliconization process is indicated as hot metal 5A in order to distinguish it from the hot metal 5 before the desiliconization process.
  • the basicity ((mass%) of the desiliconization slag 6 is used in order to prevent the dephosphorization from the dephosphorization slag 7 of the previous charge remaining in the furnace to the hot metal 5 in the desiliconization process.
  • CaO) / (mass% SiO 2 )) is adjusted appropriately.
  • the hot metal temperature is about 1300 ° C. and the FeO concentration in the desiliconization slag is about 10 to 20% by mass.
  • the basicity of the desiliconized slag 6 may be adjusted to 0.8 or more throughout the entire period of the desiliconization treatment.
  • the basicity ((mass% CaO) / (mass% SiO 2 )) of the desiliconized slag 6 can be calculated based on the following formula (1).
  • Basicity [(Remaining CaO amount in furnace (kg / molten iron-t)) + (Amount of added CaO in desiliconization treatment (kg / molten iron-t))] ⁇ [(Remaining amount of SiO 2 in furnace (kg / molten iron) -T)) + (Amount of SiO 2 produced in the desiliconization process (kg / molten iron-t))] ...
  • the amount of generated SiO 2 in the desiliconization process can be calculated from the change in the silicon concentration in the hot metal during the desiliconization process.
  • CaO-based solvent examples include quick lime, calcium carbonate, dolomite, pretreatment slag (slag produced by hot metal pretreatment (dephosphorization treatment)), converter slag (decarburization refining in a pure oxygen converter for steelmaking) Slag to be generated), ladle slag (slag present on the molten steel in the ladle, and the converter slag that flowed into the ladle at the time of steelmaking and deoxidation products such as alumina, And those formed by adding a slag modifier such as quicklime).
  • the dephosphorization slag 7 discharged outside the furnace in the refining pattern 2 can also be used as a CaO-based medium solvent.
  • the basicity of the desiliconized slag 6 after the desiliconization treatment is preferably 1.5 or less, and may be in the range of 0.8 to 1.5 as described later.
  • the one where the basicity of the desiliconization slag 6 after a desiliconization process reduces is advantageous, and it is more preferable to set it as 1.2 or less.
  • the CaO-based solvent As a method for adding the CaO-based solvent, granular and lump-like ones are charged from a hopper on the furnace, and powdery ones are added by spraying via an upper blowing lance 2 (referred to as “projection”). be able to.
  • the CaO-based solvent may be added after the desiliconization process is started, but in order to sufficiently slag the formation of the desiliconized slag 6 during the desiliconization process, the CaO-based solvent must be added in advance. It may be put in the furnace. However, in the refining pattern 1, since the pre-charged dephosphorization slag 7 remains in the furnace, it may not be necessary to add a CaO-based solvent when the silicon concentration of the hot metal 5 used in the desiliconization process is low. is there.
  • the oxygen source for the desiliconization treatment only the oxygen gas 9 from the top blowing lance 2 may be used, or iron oxide (not shown) may be used in combination with the oxygen gas 9.
  • iron oxide having a function of promoting the hatching of the CaO-based solvent. is there.
  • the converter-type smelting furnace 1 is used as a smelting vessel, strong stirring is possible, and even if the desiliconization process is performed using only the oxygen gas 9 as the oxygen source, sufficient target basicity can be removed. Silica slag 6 can be formed.
  • the decarburization reaction is gradually activated to increase the production rate of CO gas.
  • the properties of the desiliconized slag 6 are appropriate, a large amount of small CO gas bubbles are included in the desiliconized slag, and the apparent volume of the desiliconized slag 6 includes bubbles. This is a so-called forming state that increases several times as much as in the case of no.
  • the furnace body is tilted within a range in which the molten iron 5A does not flow out of the furnace port, and the desiliconization slag 6 is discharged by overflow from the furnace port.
  • the concentration of iron oxide in the slag can be adjusted so that the forming of the desiliconized slag 6 is promoted in a range where the slag is not ejected from the furnace port, and the forming can be maintained even during intermediate waste. preferable.
  • FIG. 2- (C) the side where the tap hole of the converter-type refining furnace 1 is located is located above.
  • the converter-type refining furnace 1 is tilted, and the low-basic desiliconized slag 6 containing a large amount of SiO 2 generated by the silicon removal treatment is transferred from the furnace port of the converter-type refining furnace 1 to the slag container. (Not shown).
  • the basicity of the desiliconized slag 6 to be discharged is 1.5 or less and the temperature of the desiliconized slag 6 is 1280 ° C. or more. This is to secure the fluidity of the desiliconized slag 6 and to obtain a good evacuation property and evacuation rate.
  • the rejection rate can be obtained by the following equation (2).
  • Waste rate (mass%) (exhaust slag mass) ⁇ 100 / [(slag mass generated in the desiliconization process) + (residual mass of dephosphorization slag of the previous charge)] (2) From the viewpoint of reducing the addition amount of the CaO-based solvent, it is preferable that the basicity of the desiliconized slag 6 is 1.2 or less.
  • the temperature of the desiliconized slag 6 may be lower than 1280 ° C.
  • the temperature of the desiliconized slag 6 is 1320 ° C. or higher.
  • the slag temperature after the desiliconization treatment is 1380 ° C. The following is preferable.
  • the removal rate of the desiliconized slag 6 in the intermediate removal step is preferably 30% by mass or more for the following reason. That is, in the subsequent dephosphorization process, it is necessary to adjust the basicity of the dephosphorization slag 7 to 1.5 to 3.5 in order to proceed with the dephosphorization reaction, and when the rejection rate is less than 30% by mass.
  • the amount of the CaO-based medium solvent to be added in the dephosphorization process will increase. Further, this increases the amount of dephosphorization slag 7 in the dephosphorization process, so that slag forming during the dephosphorization process cannot be suppressed, and the dephosphorization slag 7 leaks from the furnace port of the converter type refining furnace 1. There is also an increased risk of operational problems.
  • the rejection rate is preferably 80% by mass or less.
  • the mass of the desiliconized slag 6 remaining in the furnace after the intermediate waste process is calculated by subtracting the mass of the desiliconized slag 6 discharged from the total mass of the desiliconized slag 6.
  • the total mass of the desiliconized slag 6 is determined by the denominator of the above formula (2), that is, [(mass slag generated in the desiliconization process) + (residual mass of dephosphorized slag of the previous charge)].
  • the residual mass of the dephosphorization slag of the precharge is the desiliconization slag remaining in the furnace immediately after the intermediate charge step of the precharge when the precharge dephosphorization slag 7 is not discharged out of the furnace.
  • the dephosphorization slag 7 is a total value of the calculated value (estimated value) of mass 6 and the increase amount of the dephosphorization slag 7 caused by the medium solvent added in the pre-charge dephosphorization process and the generated oxide such as phosphoric acid.
  • the residual mass of the pre-charge dephosphorization slag is set to 0 (zero) or it is empirically grasped into the furnace. It is good also as a standard value of the dephosphorization slag adhesion amount.
  • the mass of the desiliconized slag 6 discharged is the weight of the desiliconized slag 6 discharged to the slag container (not shown) or the forming of the desiliconized slag 6 discharged to the slag container is calmed down ( This is determined by visual observation of the slag surface position in the slag container after subside.
  • the hot metal 5A is discharged from the furnace port together with the desiliconized slag 6 to some extent.
  • the discharge amount of the hot metal 5A is not necessarily constant.
  • the mass ratio of the hot metal 5A mixed in the desiliconized slag is a relatively stable level within a range of, for example, 5% by mass or less.
  • the mass of the molten iron 5A mixed in the discharged desiliconized slag can be calculated based on the weighed value of the discharged material using the mass ratio of pig iron obtained from the sample of the desiliconized slag 6 as a representative value. In many cases, there is no problem. Therefore, the mass of the desiliconized slag 6 discharged can be obtained by subtracting the mass of the molten iron 5A mixed in the discharged desiliconized slag from the measured value of the discharged material into the slag container.
  • the ratio of the desiliconization slag residual amount to the mass of the molten iron 5A remaining in the furnace (kg / molten iron-ton) can be obtained.
  • the residual amount of desiliconized slag 6 in the furnace immediately after the intermediate waste process is preferably 25 kg / molten-ton or less.
  • the dephosphorization process should be carried out efficiently without excessive use of the CaO-based solvent in the subsequent dephosphorization process. Is possible.
  • the amount of dephosphorization slag after the dephosphorization treatment is also within an appropriate range, the amount of slag is determined when pretreatment of the hot metal 5 of the next charge is performed without discharging the dephosphorization slag 7 and remaining in the furnace. This can reduce the risk of excessive operation and hindering operation. Accordingly, it is preferable to carry out the intermediate waste so that the residual desiliconization slag 6 in the furnace becomes 25 kg / mol-ton or less.
  • the removal rate (mass%) of the desiliconized slag 6 and the residual amount (kg / molten-ton) of the desiliconized slag 6 with respect to the molten iron 5A do not correspond one-to-one. This is because the mass of the desiliconized slag 6 is changed by charging.
  • the desiliconized slag 6 discharged out of the furnace in the intermediate waste process has high fluidity, the granular iron present in the desiliconized slag tends to settle in the hot metal. Therefore, when the desiliconized slag 6 is compared with the dephosphorized slag 7 after the dephosphorization treatment, in the desiliconized slag 6, the metal iron content mixed in the slag is reduced to about 1/10 or less. On the other hand, it is difficult to separate the metallic iron mixed in the dephosphorization slag from the dephosphorization slag 7, and most of the metal iron is not recovered as iron but is processed as the dephosphorization slag 7.
  • the hot metal 5A remaining in the converter type refining furnace is supplied with a CaO-based solvent and an oxygen source, and the hot metal 5A is dephosphorized as shown in FIG. 2- (D).
  • the basicity of the dephosphorization slag 7 in the furnace is adjusted to a range of 1.5 to 3.5, more preferably to a range of 1.8 to 3.0.
  • the oxygen source used in this dephosphorization process is mainly composed of oxygen gas 9 from the top blowing lance 2 as in the desiliconization process, but a portion of iron oxide may be used.
  • CaO-based medium solvent used in the dephosphorization treatment quick lime, calcium carbonate, or the like can be used. However, it is not limited to these, CaO contains 50 parts by mass or more with respect to a total of 100 parts by mass of components other than iron and iron oxide, and those containing other components such as fluorine and alumina as necessary, It can be used as a CaO-based medium solvent at the time of dephosphorization treatment.
  • granular and lump-shaped ones can be fed from a hopper on the furnace, and powdery ones can be projected through an upper blowing lance 2 or the like.
  • Phosphorus in the hot metal is oxidized to oxygen in the supplied oxygen source to become phosphorus oxide (P 2 O 5 ), which is formed by the incubation of the CaO-based solvent and functions as a dephosphorizing refining agent.
  • the phosphorus slag 7 is incorporated as a stable compound of 3CaO ⁇ P 2 O 5 and the dephosphorization reaction of the hot metal 5A proceeds. If the dephosphorization processing time has elapsed, or if the supply of a predetermined amount of CaO-based solvent and oxygen source has been completed, or if the dephosphorization reaction proceeds and the phosphorus concentration in the hot metal 5A reaches a predetermined level When the value is lowered, the dephosphorization process is terminated.
  • the hot metal after the dephosphorization treatment is indicated as hot metal 5B in order to distinguish it from the hot metal 5A before the dephosphorization treatment.
  • the amount of CaO-based solvent used depends on the conditions such as the residual amount of desiliconized slag 6 remaining in the furnace after the intermediate exhausting step, the target phosphorus content of the hot metal 5B after dephosphorization, and the refining temperature. It is desirable to adjust. For example, when the residual amount of desiliconized slag 6 is 15 kg / molten-ton or less, the residual amount of desiliconized slag 6 is small, and even with a relatively small amount of CaO-based solvent used, a low molten iron of 0.03% by mass or less Dephosphorization can be efficiently performed up to the medium phosphorus content.
  • the residual amount of desiliconized slag 6 exceeds 25 kg / molten-ton, a large amount of CaO-based medium is required for dephosphorization to the target phosphorus content (for example, 0.03% by mass) of molten iron 5B. It is necessary to use a solvent, and the amount of dephosphorization slag 7 becomes enormous. Further, when the residual amount of the desiliconized slag 6 is between 15 kg / molten iron-ton and 25 kg / molten-ton-ton, the usage amount of the CaO-based solvent is adjusted according to the target phosphorus content of the molten iron 5B. Accordingly, the dephosphorization treatment can be performed relatively efficiently, but the amount of the dephosphorization slag 7 is increased or decreased accordingly.
  • the converter type refining furnace 1 is tilted to the side where the outlet 4 is installed, and the hot metal 5B in the converter type refining furnace is moved to the outlet. 4 is used to pour hot water into a hot metal holding container (not shown).
  • Reference numeral 5B shown in FIG. 2- (E) is hot metal after the dephosphorization treatment.
  • dephosphorization slag 7 In the converter-type refining furnace 1 after the end of pouring, dephosphorization slag 7 remains, and a small amount of hot metal 5B also remains although not shown. In the pouring process, at the end of the pouring process, a part of the dephosphorization slag 7 flows out of the hot metal 5B flowing out from the pouring spout 4 and this dephosphorization slag 7 is unavoidably intended to flow out. In the present invention, this state is defined as the total amount of dephosphorization slag 7 remaining in the furnace.
  • the dephosphorization slag 7 is not discharged from the converter-type refining furnace 1, but the process returns to the hot metal charging process shown in FIG.
  • the desiliconization process and the dephosphorization process of the hot metal 5 are performed as described above.
  • the dephosphorization slag 7 left in the furnace is lower in temperature than the converter slag produced by decarburization refining, and the iron oxide concentration is low, so the reactivity with the hot metal 5 is relatively low. Therefore, even if the hot metal 5 is charged from above the dephosphorization slag 7 without performing the solidification treatment of the dephosphorization slag 7 by introducing the coolant, there is no problem in operation.
  • a small-sized cold iron source is fed into the converter-type refining furnace 1 from the hopper on the furnace while the converter-type refining furnace 1 is turned upright. Or after introducing a slagging material such as limestone, the converter type refining furnace 1 is tilted back and forth several times to solidify the dephosphorization slag 7 remaining in the furnace (dephosphorization slag solidification step) It does n’t matter.
  • refinement pattern 1 is carried out.
  • the entire amount of the dephosphorization slag 7 is left in the furnace and the desiliconization process of the next charge is started, so the heat amount and iron content of the decharged slag 7 of the previous charge are recovered in the desiliconization process of the next charge.
  • the CaO content in the dephosphorization slag of the previous charge can be utilized as a CaO source in the desiliconization process of the next charge. Thereby, the usage-amount of new CaO type
  • the converter type refining furnace 1 is further tilted,
  • the dephosphorization slag 7 is discharged from the furnace port to a slag storage container (not shown) so as to face directly below (exhaust process).
  • a slag accommodation container that does not contain the desiliconized slag 6 discharged in the intermediate waste disposal process.
  • the refining pattern 1 is carried out in accordance with the refining pattern 1. Charge into the converter type refining furnace. Therefore, in the next charge of the charge to which the refining pattern 2 is applied, the hot metal 5 is charged into the converter-type refining furnace 1 in a state where the total amount of dephosphorization slag 7 that can be discharged is discharged from the furnace.
  • the dephosphorization slag 7 adheres and remains on the inner wall of the converter-type refining furnace 1, but since the entire amount of dephosphorization slag 7 that can be discharged is discharged, the amount of dephosphorization slag 7 attached is small. There is no need to consider rephosphorization from the dephosphorization slag 7.
  • the CaO-based solvent used at this time is not particularly limited, but in addition to general CaO-based solvents such as quick lime and limestone, pretreatment slag (dephosphorization slag), converter slag, ladle slag, refining pattern 2 Steelmaking slag such as dephosphorization slag 7 discharged out of the furnace in the discharging step may be reused.
  • general CaO-based solvents such as quick lime and limestone, pretreatment slag (dephosphorization slag), converter slag, ladle slag, refining pattern 2 Steelmaking slag such as dephosphorization slag 7 discharged out of the furnace in the discharging step may be reused.
  • the dephosphorization slag 7 discharged out of the furnace in the refining pattern 2 discharge process has a relatively low basicity and easily hatches even in a short desiliconization process. Since it can be used in a relatively large mass without being pulverized, and pig iron contained in the dephosphorization slag can be recovered in the molten iron 5, it can be used as a CaO-based solvent used in the desiliconization process. preferable. In this case, in order to save the processing cost of the dephosphorization slag 7, the dephosphorization slag 7 is not crushed and the metal is not selected, but directly from the slag container or via a place such as a dry pit.
  • a heavy loader such as a wheel loader and put it into the iron scrap charging chute, and charge it into the converter type refining furnace 1 together with the iron scrap.
  • a heavy loader such as a wheel loader and put it into the iron scrap charging chute, and charge it into the converter type refining furnace 1 together with the iron scrap.
  • the dephosphorization slag 7 discharged to the outside of the furnace in the smelting process of the refining pattern 2 as a CaO-based medium solvent used in the desiliconization process without being pulverized.
  • the intermediate waste process shown in FIG. 2- (C) is not performed, and other processes can be performed according to the refining pattern 1.
  • the operation time can be shortened by the time of the intermediate waste process.
  • the next dephosphorization process is performed with an appropriate amount of desiliconized slag 6 remaining in the furnace, the amount of slag in the furnace can be almost accurately grasped and the CaO-based solvent can be hatched.
  • the amount of slag necessary for dephosphorization can be ensured without adding an excessive CaO-based solvent. Further, since the entire amount of the dephosphorization slag 7 is left in the furnace and the desiliconization process for the next charge is started, the next charge is the same as the case where the above-described refining pattern 1 including the intermediate evacuation process is performed in the charge. The effect of can be obtained.
  • the silicon content of the hot metal 5 used in the charge exceeds 0.70% by mass, the silicon concentration of the hot metal 5A after the desiliconization treatment may not be sufficiently lowered, and the desiliconized slag 6 is placed in the middle. Even if it is discharged, the amount of slag in the dephosphorization process increases so much that it may not be possible to perform the next charge desiliconization process while leaving the entire amount of dephosphorization slag 7 in the furnace. That is, since it may become impossible to select the refining pattern 1, it is preferable to apply the present invention to the hot metal 5 having a silicon content of 0.70% by mass or less.
  • the hot metal 5A subjected to desiliconization is discharged from the converter type refining furnace 1 without performing the treatment, and this hot metal 5A is subjected to decarburization refining performed in a pure oxygen converter for steelmaking. If the amount of desiliconized slag 6 produced is excessive and the hot water from the molten iron 5A from the converter type refining furnace 1 is disturbed, the converter type refining furnace 1 is discharged before the molten metal 5A is discharged.
  • the desiliconized slag 6 may be partially discharged from the furnace opening to the extent that there is no hindrance to the hot water, and then the hot metal 5A may be discharged. At that time, after the hot metal 5A is discharged, the converter-type refining furnace 1 is tilted in the opposite direction so that the bottom of the converter-type refining furnace 1 faces upward, and the desiliconization slag 6 is discharged from the furnace port.
  • the dephosphorization slag 7 after the dephosphorization treatment has low fluidity, it is difficult to partially discharge so as to control the residual amount of the dephosphorization slag 7 in the furnace.
  • the working time is greatly extended. Therefore, it is usually carried out by selecting either the method of discharging almost the entire amount excluding the deposit in the furnace, or the method of carrying it over to the next charge without leaving the furnace. .
  • the selection of the refining pattern 1 and the refining pattern 2 is performed as follows.
  • the predetermined value Z is a certain value set within the range of the phosphorus content analysis value of hot metal 5B of 0.030 mass% to 0.060 mass% depending on the processing conditions.
  • Predetermined value Z is used as the equipment of the converter type refining furnace 1 to be used, the refining conditions of the dephosphorization treatment of the charge and the desiliconization treatment of the next charge, the conditions and the target conditions of the components and temperature before the hot metal treatment of the next charge Depending on the conditions such as the phosphorus content of the hot metal 5B after dephosphorization, in the pre-treatment of the next charge, it may cause operational hindrance such as slag ejection and lack of dephosphorization, or the work time in intermediate waste after desiliconization As long as the dephosphorization slag 7 remains in the furnace as much as possible, it may be appropriately determined based on actual results so that the ratio of use in the next charge is not lowered.
  • the hot metal dephosphorization treatment is performed based on the past dephosphorization treatment results, etc., so that the operating conditions such as the oxygen source and the amount of CaO-based solvent used are adjusted so that the phosphorus content in the hot metal is within a predetermined target range. Adjusted and implemented.
  • the predetermined value Z is set to a value that is somewhat higher than the target range of the phosphorus content in the hot metal of the charge. Therefore, the phosphorus content in the hot metal exceeding the predetermined value Z corresponds to the case where the operating conditions of the dephosphorization treatment cannot be controlled as expected.
  • the amount of residual slag after intermediate drainage is higher than expected and the basicity of dephosphorization slag is lower than expected, the amount of slag is too high, or the basicity of slag is low.
  • the slag was excessively formed during the dephosphorization process, and the blowing source was interrupted, so that the oxygen source could not be supplied as scheduled.
  • the degassing treatment is carried out by charging the molten iron of the next charge without discharging the slag after the dephosphorization treatment. There is a risk of extending the processing time due to interruption of blowing.
  • the predetermined value Z is 0.060 mass% or less.
  • the ratio of the charge that can be used in the desiliconization process of the next charge without removing the dephosphorization slag is relatively lowered as the predetermined value Z is set lower.
  • the predetermined value Z is preferably 0.030% by mass or more.
  • the predetermined value Z in the charge is set low to reduce the risk due to the slag ejection in the next charge. Even when the phosphorus content of the hot metal after the target dephosphorization treatment in the next charge is low, it is preferable to set the predetermined value Z in the charge low.
  • the predetermined value Z is preferably determined in consideration of the above-described conditions for each charge, but a standard fixed value may be used when there is little fluctuation for each charge.
  • the refining pattern 1 and the refining pattern 2 are the same up to the pouring process shown in FIG. 2- (E). After the pouring process, the molten iron 5 of the next charge is charged without draining the dephosphorization slag 7, or the removing process is performed. It differs depending on whether the molten iron 5 of the next charge is charged after the phosphorus slag 7 is discharged. Therefore, the present invention can be applied without any problem if the phosphorus content analysis value of the hot metal 5B after the dephosphorization process is found by the completion of the hot water process.
  • the refining pattern 2 is applied when the dephosphorization reaction is not performed smoothly because the intermediate removal of the desiliconized slag 6 is not performed smoothly. That is, the dephosphorization slag 7 produced by the dephosphorization process in such a case has problems such as low basicity or excessive slag amount and low reaction efficiency. When such dephosphorization slag 7 is used in the next charge, there is a high possibility of causing adverse effects on operations by causing slag ejection due to excessive slag or increasing the amount of CaO-based solvent used. It is. If the dephosphorization reaction is not smooth, the phosphorus content of the hot metal 5B increases. Therefore, by setting an appropriate Z, the refining pattern 2 can be selected to avoid the above-described adverse effect on the next charge.
  • the pretreatment of the refining pattern 1 is repeated many times, errors may gradually accumulate in the estimated value of the amount of slag in the furnace, and the deviation from the actual situation may increase.
  • the amount of slag discharged from the intermediate waste is likely to decrease due to the influence of the operating conditions, and more easily evaluated than the actual amount. Therefore, the actual amount of slag in the furnace tends to be larger than the estimated value. Therefore, if the difference between the two becomes too large, the basicity of the dephosphorization slag decreases, which is a disadvantageous condition for the dephosphorization treatment, and the phosphorus content of the hot metal 5B increases and is higher than the predetermined value Z. Become. In such a case, by applying the refining pattern 2, it is possible to reduce the error of the estimated value of the in-furnace slag amount and perform appropriate refining control again.
  • the refining pattern 2 is applied to prevent the dephosphorization slag 7 from remaining in the furnace.
  • the dephosphorization treatment step is performed. Whether or not the dephosphorization slag 7 in the furnace is discharged out of the furnace is determined based on the analysis value of the phosphorus content of the hot metal 5B. In other words, since the refining pattern 1 or 2 is determined based on the phosphorus content analysis value of the hot metal 5B after the phosphorus treatment step, the hot metal 5 that is continuously performed over a plurality of charges is determined. Even if it is difficult to accurately grasp the mass and composition of the slag remaining in the furnace during the pretreatment operation, the hot metal 5 is subjected to an optimal pretreatment method according to the situation. Can be efficiently desiliconized and dephosphorized efficiently.
  • the hot metal preliminary treatment (invention example 1) performed by applying the present invention with the predetermined value Z being 0.040 mass%
  • the predetermined value Z is 0.050 mass%
  • Hot metal pretreatment performed by applying the present invention Example 2 of the present invention
  • Hot metal pretreatment performed by applying only the refining pattern 1 Comparative Example 1
  • Hot metal pretreatment performed by applying only the refining pattern 2 Comparative Example 2
  • the molten iron is charged into another converter-type refining furnace, that is, a pure oxygen converter for steelmaking (hereinafter simply referred to as “converter”), decarburized and refined, Melted.
  • converter-type refining furnace that is, a pure oxygen converter for steelmaking
  • the silicon content of the hot metal before the desiliconization treatment is 0.20 to 0.70 mass%, and the phosphorus content of the hot metal is 0.100 to 0.120 mass%.
  • the hot metal temperature is in the range of 1260 to 1350 ° C., and the frequency distributions of the silicon content in the hot metal, the phosphorus content in the hot metal and the hot metal temperature are significant between the inventive examples 1 and 2 and the comparative examples 1 and 2. There was no difference.
  • the amount of iron scrap charged into the pretreatment converter-type smelting furnace before hot metal charging is based on the actual value in each test period, and the hot metal temperature at the end of the desiliconization process is in the range of 1300 to 1350 ° C It was adjusted in the range of 50 to 100 kg / molten iron-ton so as to be inside.
  • the hot metal after this pretreatment was decarburized and refined, no iron scrap was charged into the converter for decarburization and refinement.
  • both the refining pattern 1 and the refining pattern 2 were removed from the furnace during the desiliconization process in order to improve the exhaustability at the time of intermediate exhaust after the desiliconization process.
  • the conditions for acid delivery were adjusted to promote the formation of silica slag.
  • refining is interrupted once, and sedative material is added to form. After refining, refining resumed. In such a case, the processing time was extended.
  • the target value of the phosphorus content of the hot metal after the dephosphorization process is set to 0.030% by mass or less, a CaO-based solvent is supplied, and the basicity is 1.5-3.
  • the dephosphorization process was performed while adjusting in the range of 0.
  • As CaO-based solvent dephosphorization slag discharged in the case of the refining pattern 2 was used in Examples 1 and 2 of the present invention in addition to quick lime (CaO).
  • the discharged dephosphorization slag is 2-5 tons / charge in consideration of the balance between the generated amount and the consumed amount, and is charged with iron scrap along with the iron scrap at the next charge of the charge applying the refining pattern 2 and other charges. It was charged into a converter-type refining furnace via a charging chute and used as a CaO-based solvent for desiliconization.
  • the hot metal used for decarburization refining was pretreated as much as possible, desiliconization and dephosphorization, but in order to continue continuous casting of multiple charges in the subsequent continuous casting process, a converter for decarburization refining.
  • a converter for decarburization refining When the supply of hot metal to the hot metal was not in time, the hot metal that was not subjected to the pretreatment or the hot metal that was preliminarily completed in the middle was charged into a converter for decarburization and decarburization.
  • an amount of iron scrap equivalent to that charged into the converter type refining furnace for pretreatment is charged before the hot metal is charged. It was charged in a converter for decarburization refining.
  • decarburization refining the amount of quick lime, which is a dephosphorizing refining agent, was adjusted according to the phosphorus concentration of the hot metal charged in the converter for decarburization refining.
  • the decarburization refining was carried out at an average frequency of about 40 charges / day, and there was no significant difference in the decarburization refining frequency depending on each test period.
  • the predetermined value Z is set to 0.040% by mass, and in the present invention example 2, the predetermined value Z is set to 0.050% by mass, and the phosphorus content of the hot metal after the dephosphorization treatment of the charge.
  • the refining pattern 1 or the refining pattern 2 was selected, and after the hot metal for the charge was pretreated, the hot metal for the next charge was charged and the hot metal was preliminarily treated.
  • the desiliconization slag residual amount (Q) in the furnace immediately after the intermediate evacuation process is calculated based on the residual amount of dephosphorization slag in the furnace before the desiliconization process calculated from the results of the previous charge and the desiliconization of the charge.
  • Table 1 shows the total amount of iron scrap (kg / molten iron-ton) to be used in the pretreatment converter-type refining furnace and decarburization-refining converter, pre-treatment converter-type refining furnace, and decarburization.
  • the ratio of the number of decarburization refining charges to the number of decarburization charges is shown for each test period.
  • Comparative Example 1 compared with Comparative Example 2, the amount of scrap iron increased and the iron yield was improved, and the merit and desorption of heat were reduced by reusing the dephosphorization slag for the next charge at a high temperature.
  • the merit of recovering iron in phosphorus slag was obvious.
  • the total amount of quicklime used was the same as that of Comparative Example 2 in spite of the fact that the pre-charged dephosphorization slag could be used as a source of lime in the desiliconization treatment, and the reduction of quicklime usage was not obtained.
  • Examples 1 and 2 of the present invention there is no decrease in the pretreatment ratio as in Comparative Example 1 or an increase in the phosphorus content of the hot metal after the dephosphorization treatment. It could be reused for the next charge.
  • this invention example 1 and 2 compared with the comparative example 1 and the comparative example 2, the total usage-amount of quicklime can be reduced significantly, and it confirms that a preliminary process is efficiently performed with respect to hot metal. did it.

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  • Materials Engineering (AREA)
  • Metallurgy (AREA)
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Abstract

La présente invention concerne un procédé de prétraitement de fer fondu dans lequel, à l'aide d'un fourneau d'affinage de type convertisseur, un traitement de désiliciation et un traitement de déphosphoration, destinés au fer fondu prélevé d'un haut fourneau, sont consécutivement mis en œuvre, le traitement de désiliciation et le traitement déphosphoration étant effectués de manière efficace même si la détermination avec précision, de l'état de la masse et de la composition du laitier restant dans un fourneau, fut difficile. À l'aide d'un fourneau d'affinage (1) de type convertisseur, le fer fondu est prétraité par l'exécution des étapes suivantes dans l'ordre donné : une étape de traitement de désiliciation destinée au fer fondu (5) ; une étape de décharge de dépôt intermédiaire servant à décharger le laitier désilicié (6) produit lors de l'étape de traitement de désiliciation ; une étape de traitement de déphosphoration durant laquelle un fer fondu (5A), qui est amené à rester à l'intérieur du fourneau d'affinage, est soumis à un traitement de déphosphoration ; et une étape de prélèvement servant à prélever un fer fondu (5B) qui a été soumis au traitement de déphosphoration. Après l'étape de prélèvement, l'évacuation ou non du laitier déphosphorisé (7), produit lors de l'étape de déphosphoration, vers l'extérieur du fourneau, est déterminée en fonction d'une valeur d'analyse de la teneur en phosphore du fer fondu (5B) après le traitement de déphosphoration d'une charge. Ensuite, le fer fondu d'une charge suivante est chargé dans le fourneau de raffinage et le prétraitement est réalisé.
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