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WO2017119392A1 - Agent de déphosphoration de fer en fusion, agent d'affinage, et procédé de déphosphoration - Google Patents

Agent de déphosphoration de fer en fusion, agent d'affinage, et procédé de déphosphoration Download PDF

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Publication number
WO2017119392A1
WO2017119392A1 PCT/JP2016/089082 JP2016089082W WO2017119392A1 WO 2017119392 A1 WO2017119392 A1 WO 2017119392A1 JP 2016089082 W JP2016089082 W JP 2016089082W WO 2017119392 A1 WO2017119392 A1 WO 2017119392A1
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WO
WIPO (PCT)
Prior art keywords
mass
dephosphorization
cao
sio
converter
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/JP2016/089082
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English (en)
Japanese (ja)
Inventor
昌平 柿本
祐志 野崎
義明 権田
明人 清▲瀬▼
直樹 古河
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Steel Corp
Original Assignee
Nippon Steel and Sumitomo Metal 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.)
Filing date
Publication date
Application filed by Nippon Steel and Sumitomo Metal Corp filed Critical Nippon Steel and Sumitomo Metal Corp
Priority to JP2017560372A priority Critical patent/JP6481774B2/ja
Priority to CN201680045089.0A priority patent/CN107849625A/zh
Priority to KR1020187002603A priority patent/KR102105353B1/ko
Publication of WO2017119392A1 publication Critical patent/WO2017119392A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C1/00—Refining of pig-iron; Cast iron
    • C21C1/02—Dephosphorising or desulfurising
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C1/00—Refining of pig-iron; Cast iron
    • C21C1/02—Dephosphorising or desulfurising
    • C21C1/025—Agents used for dephosphorising or desulfurising
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
    • C21C5/28—Manufacture of steel in the converter
    • C21C5/36—Processes yielding slags of special composition
    • 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
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/04—Removing impurities by adding a treating agent
    • C21C7/064—Dephosphorising; Desulfurising
    • C21C7/0645—Agents used for dephosphorising or desulfurising
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • the present invention relates to a hot metal dephosphorization method using a top-bottom converter, which can efficiently produce low phosphorus steel even in a refining process with a short blowing time,
  • the present invention relates to an agent and a dephosphorization method.
  • hot metal dephosphorization is widely performed by a method in which the hot metal is treated under low temperature conditions in a hot metal stage, which is thermodynamically advantageous.
  • a top-bottom converter is suitable for hot metal dephosphorization. This is because, as an oxidant necessary for dephosphorization, gaseous oxygen with less heat loss than a solid oxidation source can be blown from the top blowing lance to the hot metal at high speed.
  • Patent Documents 1 and 2 are known in which a refining agent containing calcium ferrite is added to the hot metal charged in the top-bottom blow converter.
  • Calcium ferrite is a dephosphorization agent composed of a compound of CaO and Fe 2 O 3 and has a higher dissolution rate in dephosphorization slag as compared with quick lime generally used as a dephosphorization agent in hot metal dephosphorization process. Dephosphorization reaction can be promoted.
  • Patent Document 3 discloses a dephosphorizing agent to which Na 2 O is added in order to improve the meltability of calcium ferrite.
  • Patent Document 4 discloses a hatching accelerator in which any one of alumina powder, iron oxide powder, soda ash, and soda glass powder is contained in a refining flux containing 50% by weight or more of quicklime powder.
  • JP 2013-163844 A JP2013-064167A JP 2012-12680 A JP 2001-348610 A
  • the normal calcium ferrite used in the dephosphorization treatment disclosed in Patent Documents 1 and 2 has a liquidus temperature of about 1400 ° C., which is higher than 1200 to 1350 ° C., which is the temperature of the hot metal in the converter. high. This is because solid calcium ferrite dissolves in the dephosphorization slag of the liquid generated by the oxidation reaction of oxygen and Si or Fe in the hot metal supplied from the top blowing lance. It is conceivable that the ferrite is not sufficiently melted, dephosphorization becomes insufficient, and the blowing is completed in a state where [P] (mass% of P dissolved in the steel) does not reach the target value.
  • the blowing time is about 10 minutes, and after 35% of the total blowing time has elapsed, calcium ferrite starts to be added, and the addition is completed until 80% of the total blowing time has elapsed.
  • the technology to do is described. However, for example, when blowing in a short time of 4 minutes or less, there is a concern that the method of Patent Document 2 may cause insufficient melting of calcium ferrite and deteriorate the dephosphorization efficiency.
  • Patent Document 3 describes calcium ferrite containing Na 2 O, but does not describe a dephosphorization method using the same, and a dephosphorization method suitable for a short blowing time is unknown. is there. Further, according to experiments using the top-bottom blow converter of the present inventors, when the dephosphorization agent described in Patent Document 3 is used for a short time of about 4 minutes, calcium ferrite is not sufficient. It did not melt, the phosphorus removal efficiency was insufficient, and it was difficult to produce low phosphorus steel with [P] ⁇ 0.02%.
  • the refining flux mainly composed of quick lime powder is not sufficiently dissolved in a short time of about 4 minutes, and the dephosphorization efficiency is insufficient. This is because quick lime, alumina, iron oxide, and the like contained in the refining flux each have a high melting point and a low melting rate of the entire refining flux.
  • the present inventors have intensively studied, and by adding Al 2 O 3 to calcium ferrite and further optimizing these concentrations, the refining agent can be sufficiently dissolved even in a short time of blowing. And found that low phosphorus steel can be efficiently produced. Further, in addition to Al 2 O 3 , further studies were made to contain SiO 2 and Na 2 O.
  • the following invention was devised.
  • the molten iron dephosphorizing agent according to (1) which contains 1 to 10% by mass of SiO 2 and has a ratio of (SiO 2 % by mass) / (CaO mass%) of 0.04 to 0.3.
  • Further (Na 2 O wt%) / (Al 2 O 3 wt%) ratio contains Na 2 O of from 0.1 to 2.0 as described in any one of (1) or (2) Molten iron dephosphorizer.
  • a refining agent comprising the dephosphorizing agent according to any one of (1) to (3).
  • (5) (4) The refining agent described in (4) is added to the converter to perform dephosphorization of the hot metal, and the charging (CaO) / (SiO 2 ) ratio is 1.3 to 2.0. Dephosphorization method for molten iron.
  • (6) The hot metal dephosphorization method according to (5), wherein the CaO mass contained in the calcium ferrite is 20% or more of the CaO mass contained in the scouring agent.
  • the hot metal dephosphorization method according to (5) wherein the refining agent is charged into the converter before the hot metal is charged.
  • the calcium ferrite in the present invention a compound mainly containing CaO and Fe 2 O 3, 6 in the ratio weight ratio of CaO and Fe 2 O 3: 4 ⁇ 3 : a 7, CaO
  • the sum of mass% and Fe 2 O 3 mass% refers to 70 mass% or more.
  • Calcium ferrite is produced, for example, using quick lime and iron ore as raw materials, and a mixture of these is completely melted in a melting furnace, and after cooling, it is ground into a lump of about 1 to 50 mm.
  • low phosphorus steel refers to steel whose [P] at the slab stage is 0.02% or less, and efficient means that dissolved calcium ferrite sufficiently contributes to dephosphorization.
  • short-time blowing refers to blowing with a blowing time of about 2 to 6 minutes.
  • the present inventors added various compounds to CaO and Fe 2 O 3 in order to improve the meltability of calcium ferrite in the dephosphorization process of the top-bottom blown converter, and various calcium ferrites that were completely melted in a melting furnace. It was created. Also, CaO and Fe 2 O 3 and / or Al 2 O 3 were mixed and formed into a pellet at normal temperature (hereinafter referred to as pellet). Next, using a high-temperature microscope equipped with an infrared gold image furnace, the calcium ferrite and pellets were heated at a rate of temperature increase of 200 ° C./min, and the melting start temperature and the melting end temperature were measured.
  • CFA calcium ferrite composed of CaO, Fe 2 O 3 and Al 2 O 3
  • CF calcium ferrite composed of ordinary CaO and Fe 2 O 3
  • the liquidus temperature of CFA is estimated to be 1350 ° C or less from the melting end temperature and is lower than the liquidus temperature of CF (about 1400 ° C).
  • the use of CFA and the use of CF were considered to increase the dissolution rate and promote dephosphorization.
  • Al 2 O 3 increases the viscosity of the converter slag, if the Al 2 O 3 concentration in the converter slag becomes too high, rapid slag forming occurs in the converter, and slag is generated from the converter furnace port.
  • the frequency of splattering increases, and blowing must be interrupted.
  • the present inventors thus situation investigated proper concentration of Al 2 O 3 to prevent such, by the Al 2 O 3 calcium ferrite and 20% by mass or less to suppress the frequency of slopping, I found that I could operate without interrupting blowing.
  • the Al 2 O 3 concentration is too low, the dissolution rate of calcium ferrite is small, and it is difficult to produce low phosphorus steel by short-time blowing, so the Al 2 O 3 concentration is 2% by mass or more. It was. Furthermore, the present inventors have confirmed that a higher effect can be exhibited by setting the Al 2 O 3 concentration to 4 to 12% by mass.
  • the dissolution rate of calcium ferrite increases by increasing the Al 2 O 3 concentration in calcium ferrite, the CaO concentration in calcium ferrite necessary for dephosphorization becomes relatively low.
  • the present inventors have intensively studied and found that low phosphorus steel can be produced by setting the (Al 2 O 3 mass%) / (CaO mass%) ratio to 0.04 to 0.5. confirmed. When the (Al 2 O 3 mass%) / (CaO mass%) ratio is less than 0.04, the dissolution rate of calcium ferrite is low and dephosphorization is insufficient.
  • the present inventors conducted a test using a high-temperature microscope equipped with the above-described infrared gold image furnace, and obtained calcium ferrite containing CaO, Fe 2 O 3 , Al 2 O 3 and Na 2 O (hereinafter referred to as CFAN). Revealed that the melting start temperature and the melting end temperature are lower than those of CFA. This is presumably because Na 2 O has the effect of lowering the liquidus temperature and solidus temperature of CFA, and the liquidus temperature of CFAN was estimated to be 1330 ° C. or less from the melting end temperature.
  • the present inventors conducted an experiment using a high-temperature microscope equipped with the above-described infrared gold image furnace, and obtained calcium ferrite composed of CaO, Fe 2 O 3 , Al 2 O 3 and SiO 2 (hereinafter referred to as CFAS).
  • the melting start temperature and the melting end temperature are lower than those of CF. This was considered because SiO 2 had the effect of lowering the liquidus temperature and solidus temperature of CF.
  • SiO 2 reduces the basicity of converter slag, if the SiO 2 concentration of converter slag becomes too high, the progress of the dephosphorization reaction is suppressed, and the target [P] level at the end of blowing Can not be satisfied.
  • the present inventors investigated an appropriate SiO 2 concentration for preventing such a situation, and confirmed that the target [P] level was satisfied by making SiO 2 in calcium ferrite 10 mass% or less. .
  • the SiO 2 concentration is too low, the effect to lower the melting temperature could not be confirmed, and the SiO 2 concentration of 1% by mass or more. Furthermore, the present inventors have confirmed that a higher effect can be exhibited by setting the SiO 2 concentration to 2 to 5% by mass.
  • the present inventors diligently studied about the proper composition of SiO 2 and CaO in CFAS, and by setting the ratio of (SiO 2 mass%) / (CaO mass%) to 0.04 to 0.3, low It was confirmed that phosphorus steel could be melted. When the (SiO 2 mass%) / (CaO mass%) ratio is less than 0.04, the dissolution rate of calcium ferrite is low and dephosphorization is insufficient. If the (SiO 2 mass%) / (CaO mass%) ratio is greater than 0.3, the CaO concentration is too low and the dephosphorization is worsened. In addition, the present inventors have confirmed that by controlling the (SiO 2 mass%) / (CaO mass%) ratio to 0.1 to 0.3, a higher effect is exhibited and further dephosphorization is promoted. did.
  • the present inventors conducted an experiment using a high-temperature microscope equipped with the above-described infrared gold image furnace, and obtained calcium ferrite containing CaO, Fe 2 O 3 , Al 2 O 3 , SiO 2 and Na 2 O (hereinafter referred to as CFASN). ) Revealed that the melting start temperature and the melting end temperature were even lower than CFAS. This was thought to be because Na 2 O had the effect of lowering the liquidus temperature and solidus temperature of CFAS.
  • Examples of the Al 2 O 3 source for producing CFA include aluminum ash, alumina-based refractories, and steelmaking slag containing Al 2 O 3.
  • Examples of the SiO 2 source for producing CFAS include peridotite, pumice, SiO 2 There are steelmaking slag including 2 .
  • Examples of Na 2 O sources for CFAN and CFASN include Na 2 CO 3 , soda lime glass, and sodium metasilicate.
  • the refining agent in the dephosphorization treatment in the top-bottom blowing converter, by using calcium ferrite containing Al 2 O 3 at an appropriate concentration, the refining agent is sufficiently dissolved even in a short time of blowing. It is possible to melt low phosphorus steel efficiently. Furthermore, dephosphorization can be further promoted by adding an appropriate amount of Na 2 O and / or SiO 2 in addition to Al 2 O 3 .
  • the scrap 2 is charged into the converter 1.
  • a refining agent 3 containing at least one of CFA, CFAN, CFAS, and CFASN, which are dephosphorizing agents according to the present invention is charged into the furnace.
  • CFA, CFAN, CFAS, and CCASN may have a particle size of about 1 to 50 mm, preferably about 5 to 35 mm.
  • the charging basicity of the converter slag when using CFA, CFAN, CFAS, CFASN is preferably 1.3 to 2.0.
  • the charge basicity refers to “the total amount of CaO contained in the auxiliary raw material supplied into the converter” as a molecule, and “the total amount of SiO 2 contained in the auxiliary raw material supplied into the converter” and “ Si contained in the molten iron and scrap is a number of the ratio is calculated the sum of the SiO 2 mass "in the case of the oxidized to the total SiO 2 as a denominator.
  • the amount of CaO supplied from calcium ferrite is 20% or more of the total CaO mass contained in the refining agent 3 supplied into the converter. Is preferred.
  • the hot metal 4 is charged into the furnace (FIG. 1 (b)), and then blown by blowing oxygen from the lance 5 into the hot metal 4 (FIG. 1 (c)). ).
  • Blowing causes phosphorus in hot metal 3 to react with oxygen and CaO in slag and shift to the slag side.
  • quick lime as a CaO source has a high melting point, and the dissolution rate at the hot metal temperature during refining is small.
  • the dephosphorization agents CFA, CFAN, CFAS, and CFASN according to the present invention melt at the hot metal temperature, so the dissolution rate. Therefore, dephosphorization of hot metal can be promoted by increasing the CaO concentration in the slag early.
  • the charging of the refining agent 3 containing any one of CFA, CFAN, CFAS, and CCASN is effective even after the hot metal 4 is charged in the converter, but the refining agent is charged before the hot metal 4 is charged.
  • 3 is preferably charged. This is to promote dissolution of CFA, CFAN, CFAS, and CFASN by utilizing the stirring force when the molten iron 4 is charged.
  • only CFA, CFAN, CFAS, and CCASN among the refining agents may be charged before the molten iron 4 is charged, and other materials of the refining agent may be charged at the time of blowing.
  • Calcium ferrite composed of CaO and Fe 2 O 3 is a compound that has improved the melting property of CaO as described above, and it is well known that it melts easily against quicklime and exhibits a dephosphorization effect.
  • Al 2 O 3 which is such a dephosphorizing agent or calcium ferrite containing SiO 2 or Na 2 O, the melting point is further lowered, and the dephosphorizing effect can be enhanced.
  • the decarburization is performed in another furnace after dephosphorization, and the converter is tilted after dephosphorization, which is called MURC (Multi-Refining Converter) method.
  • MURC Multi-Refining Converter
  • the blowing time during dephosphorization is usually as short as 4 minutes, and even in such a case, the dephosphorizing agent according to the present invention is used. According to the dephosphorization method, the dephosphorization process can be performed efficiently.
  • dephosphorization treatment in a converter was performed.
  • the conditions for the dephosphorization treatment are as follows: [P] before dephosphorization is 0.1%, blowing time is 3 to 4 minutes, charging basicity is 1.8, and the amount of calcium ferrite used is 10 kg / t.
  • the product [P] in the table is [P] at the slab stage.
  • the charging timing is the timing at which calcium ferrite is charged into the converter, and is “before hot metal charging” or “after hot metal charging”.
  • 1-No. 9 achieved the product [P] ⁇ 0.02%.
  • No. 9 was a product [P] ⁇ 0.015%, and it was found that it showed a better dephosphorization ability.
  • No. which is a comparative example In all of 10 to 16, the product [P]> 0.02%, and dephosphorization was insufficient.
  • no. No. 10 has an Al 2 O 3 content of less than 2% by mass, and dissolution of calcium ferrite was insufficient. No. No. No.
  • No. which is a dephosphorizing agent according to the present invention. 6 and no. 7 has a ratio of Al 2 O 3 of 2 to 20% by mass, (Al 2 O 3 % by mass) / (CaO mass%) of 0.04 to 0.5, SiO 2 of 1 to 10% by mass, (SiO 2 (Mass%) / (CaO mass%) ratio is 0.04 to 0.3, the melting of calcium ferrite is promoted by Al 2 O 3 and SiO 2, and the rate of supplying CaO to the dephosphorized slag is high. It seems that dephosphorization was promoted. On the other hand, no. In No.
  • No. No. 16 has an Al 2 O 3 concentration of less than 2% by mass and SiO 2 of 10% by mass or more, and it is considered that dephosphorization was insufficient because the basicity of slag was lowered by SiO 2 .
  • the present invention can be applied to a dephosphorization processing method in which steel-containing scrap and molten iron are charged into a smelting furnace and blown in a steelmaking process to melt the molten steel.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Refinement Of Pig-Iron, Manufacture Of Cast Iron, And Steel Manufacture Other Than In Revolving Furnaces (AREA)
  • Carbon Steel Or Casting Steel Manufacturing (AREA)

Abstract

L'invention concerne un agent de déphosphoration de fer en fusion, contenant 2 à 20 % en masse de Al2O3, le reste étant constitué de ferrite de calcium et d'impuretés, et le rapport ((Al2O3 en masse) / (CaO % en masse) s'établissant à 0,04-0.5. La déphosphoration du fer en fusion est effectuée par addition d'un agent d'affinage contenant ledit agent de déphosphoration dans un four convertisseur.
PCT/JP2016/089082 2016-01-05 2016-12-28 Agent de déphosphoration de fer en fusion, agent d'affinage, et procédé de déphosphoration Ceased WO2017119392A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2017560372A JP6481774B2 (ja) 2016-01-05 2016-12-28 溶鉄の脱りん剤、精錬剤および脱りん方法
CN201680045089.0A CN107849625A (zh) 2016-01-05 2016-12-28 铁水的脱磷剂、精炼剂以及脱磷方法
KR1020187002603A KR102105353B1 (ko) 2016-01-05 2016-12-28 용선의 탈린제, 정련제 및 탈린 방법

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JP2016-000488 2016-01-05
JP2016000488 2016-01-05

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WO2017119392A1 true WO2017119392A1 (fr) 2017-07-13

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JP (1) JP6481774B2 (fr)
KR (1) KR102105353B1 (fr)
CN (1) CN107849625A (fr)
TW (1) TWI609839B (fr)
WO (1) WO2017119392A1 (fr)

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CN116622939A (zh) * 2023-06-29 2023-08-22 中天钢铁集团有限公司 一种降低转炉钢铁料消耗的冶炼方法

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WO2023017674A1 (fr) * 2021-08-10 2023-02-16 Ｊｆｅスチール株式会社 Dispositif d'estimation de vitesse de fusion de source de fer froide, dispositif de commande de four d'affinage de type convertisseur, procédé d'estimation de vitesse de fusion de source de fer froide et procédé d'affinage de fer fondu
CN113943844B (zh) 2021-10-19 2022-04-15 北京科技大学 一种铁水罐脱磷-转炉单脱碳的炼钢方法
CN114657326B (zh) * 2022-03-30 2024-04-02 北京科技大学 一种脱磷剂及其应用
CN114990276A (zh) * 2022-07-04 2022-09-02 北京科技大学 一种铁水同时预脱硫预脱磷的方法
KR102775761B1 (ko) 2024-02-20 2025-03-04 조선래 지금 부착 방지용 이형 코팅 조성물

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