JP4894325B2 - Hot metal dephosphorization method - Google Patents

Description

  The present invention relates to a hot metal dephosphorization method that is performed by blowing oxygen gas from an upper blowing lance onto a hot metal bath surface in a converter-type refining vessel.

In producing molten steel by decarburizing and refining the hot metal discharged from the blast furnace in the converter, conventionally, a preliminary dephosphorization process was performed at the hot metal stage to remove some phosphorus in the hot metal, and then the converter Steelmaking methods for decarburization and refining have been developed. In this preliminary dephosphorization treatment, an oxygen source such as oxygen gas or solid iron oxide is added together with a dephosphorizing refining agent mainly composed of lime (hereinafter referred to as “CaO”). That is, phosphorus in the hot metal is oxidized by the added oxygen source to form a phosphor oxide (P ₂ O ₅ ), and this phosphor oxide is absorbed and fixed with a CaO-based dephosphorizing refining agent to perform a dephosphorization reaction. Progressing. In addition to reacting with the phosphorus in the hot metal, the added oxygen source reacts with carbon and silicon, which raises the hot metal temperature. However, the dephosphorization reaction is thermodynamically favored at lower temperatures. The material was added and the hot metal temperature after processing was controlled at around 1300 ° C.

  When hot metal dephosphorization is performed, if the smelting container used is a ladle type container or a torpedo type container, the stirring force is weak, and the injection lance is often immersed in the hot metal, and the coolant It is practically impossible to add a cold iron source such as iron scrap, but in the case of a converter-type smelting vessel, the stirring force by the bottom blowing gas is large and it is not necessary to immerse the lance. Therefore, the cold iron source can be charged.

  In view of this, several methods have been proposed in which a cold iron source is dissolved during preliminary dephosphorization using a converter-type smelting vessel. For example, in Patent Document 1, when performing dephosphorization of hot metal using a converter-type refining vessel, after the molten iron is charged into the refining vessel, a dephosphorizing refining agent and lightweight scrap are added, and then A method has been proposed in which oxygen gas is supplied from an upper blowing lance, and a solid oxygen source is added at the end of the dephosphorization treatment to keep the hot metal temperature below 1400 ° C.

Further, in Patent Document 2, when performing dephosphorization of hot metal using a converter-type refining vessel, a part of the dephosphorizing refining agent and iron scrap are added to the hot metal, A dephosphorization method is proposed in which oxygen gas is blown up from the mouth and oxygen gas is blown up to dissolve iron scrap, and then the supply of carbon powder is stopped, and then the remaining dephosphorizing refining agent is added. Has been.
Japanese Patent Laid-Open No. 1-147011 Japanese Patent Laid-Open No. 2-205614

  However, the above prior art has the following problems. That is, the hot metal temperature before the start of dephosphorization is about 1300 ° C. In Patent Document 1 and Patent Document 2, since iron scrap is added to the hot metal before the start of the dephosphorization process, the hot metal temperature is lowered by the iron scrap. In addition, the hatching of the dephosphorizing refining agent added at the same time is delayed, thereby preventing the absorption of the phosphorus oxide produced by the reaction between the added oxygen source and phosphorus in the hot metal into the dephosphorizing refining agent, The dephosphorization reaction does not proceed. Due to the oxidation reaction by the supply of oxygen gas, the hot metal temperature will eventually rise and the dephosphorization reaction will proceed, but there will also be a problem that the dephosphorization treatment time becomes longer and the productivity is lowered.

  The present invention has been made in view of the above circumstances, and its object is to perform dephosphorization of hot metal by blowing oxygen gas from the top blowing lance onto the hot metal bath surface using a converter type refining vessel. In this case, the present invention provides a hot metal dephosphorization method capable of efficiently dephosphorizing without deteriorating the dephosphorization reaction even if a cold iron source such as iron scrap is blended, and without reducing the productivity. That is.

The hot metal dephosphorization processing method according to the first aspect of the present invention for solving the above-mentioned problem is the addition of a dephosphorization refining agent mainly composed of CaO to the hot metal contained in the converter type refining vessel, and the oxygen gas is increased. In the dephosphorization treatment method for hot metal, the dephosphorization refining agent added by blowing is hatched to form slag, and the dephosphorization treatment is performed on the hot metal, and the dephosphorization defined by the following formula (1): Using hot metal having an initial hot metal temperature (T ₁ ) of 1200 to 1330 ° C. before treatment, the hot metal is put in the refining vessel at any time from when 30% of the dephosphorization time has elapsed until 90% has passed. A hot iron source is added on top to adjust the hot metal temperature at the end of dephosphorization to 1400 ° C. or lower . However, in the formula (1), T ₁ is the initial hot metal temperature (° C.) before the dephosphorization treatment, [Si] is the silicon concentration (mass%) in the hot metal, and HMR is the initial hot metal mixture ratio ( Hot metal mass / (Mold iron mass + Cold iron source mass added before refining)).

  In the hot metal dephosphorization method according to the second invention, in the first invention, the cold iron source is continuously added from the time when 30% of the dephosphorization time has elapsed to the time when 90% has elapsed. It is characterized by this.

Dephosphorization method hot metal according to the third invention, Hiyatetsu added the time the first or second inventions in Oite, 90% from the time 30% of the dephosphorization refining time has elapsed elapsed The particle size of the source is 20 mm or less.

  According to the present invention, cold iron sources such as iron scrap and magnetic separation scrap are mainly introduced in the latter half of the dephosphorization refining in which the hot metal temperature rises. The hatching of the dephosphorization refining agent mainly composed of CaO is promoted from the initial stage of phosphorus refining, and the dephosphorization reaction can proceed with high efficiency from the initial stage of dephosphorization. As a result, it is possible to increase the amount of cold iron source used without extending the dephosphorization processing time, and bring about industrially beneficial effects such as resource saving, energy saving, and productivity improvement.

  Hereinafter, the present invention will be described in detail with reference to the accompanying drawings. FIG. 1 is a schematic cross-sectional view showing an example of a converter-type refining facility used when carrying out the hot metal dephosphorization method according to the present invention.

  As shown in FIG. 1, a converter-type refining equipment 1 has a converter-type refining vessel, that is, a furnace body 2, whose outer shell is composed of an iron shell 4 and a refractory 5 is enforced inside the iron shell 4. An upper blow lance 3 made of steel, which is inserted into the furnace body 2 and is movable in the vertical direction, is provided. At the upper part of the furnace body 2, a hot water outlet 6 is provided for discharging the molten iron 15 accommodated after refining, and a bottom blowing tuyere 7 for blowing the stirring gas 18 into the furnace bottom of the furnace body 2. Is provided. The bottom blowing tuyere 7 is connected to a gas introduction pipe 8. An oxygen gas pipe 9 is connected to the top blowing lance 3, and oxygen gas is supplied from the top blowing lance 3 to the inside of the furnace body 2 through the oxygen gas pipe 9 at an arbitrary flow rate. .

  The top blowing lance 3 is connected to a dispenser 11 that contains a dephosphorization refining agent 17 mainly composed of CaO via a transfer pipe 19, while the dispenser 11 branches off from the oxygen gas pipe 9. An oxygen gas pipe 9A and a nitrogen gas pipe 10 are connected. That is, the oxygen gas and nitrogen gas supplied to the dispenser 11 function as a transfer gas for the dephosphorization refining agent 17 accommodated in the dispenser 11, and from the tip of the upper blowing lance 3 via the transfer pipe 19. The dephosphorizing refining agent 17 can be sprayed and supplied (also referred to as “projection”) toward the bath surface of the hot metal 15 accommodated in the furnace body 2. The oxygen gas pipes 9 and 9A are respectively provided with flow rate control valves 12 and 13, and the nitrogen gas pipe 10 is provided with a flow rate control valve 14, and oxygen gas is supplied from the upper blow lance 3 at an arbitrary flow rate. Oxygen gas or nitrogen gas can be blown in as a carrier gas through the dispenser 11 at an arbitrary flow rate. In this case, instead of nitrogen gas, various gases such as Ar gas and carbon dioxide can be used as the carrier gas. Whether the oxygen gas or the gas other than oxygen gas such as nitrogen gas is used as the carrier gas may be determined as appropriate from the state of refining.

  Above the furnace main body 2, a cold iron source such as iron scrap and magnetic separation scrap, and a hopper that contains auxiliary raw materials such as quick lime, iron ore, coke, converter slag, and casting slag were contained in the hopper. A cutting device, a weighing device, and a chute for cutting out and adding these cold iron sources and auxiliary materials to the furnace main body 2 are installed, but are omitted in FIG. Here, magnetic waste is a slag-mixed slag that is obtained by cooling the slag generated by hot metal dephosphorization and decarburization refining with cooling water, etc., crushing and classifying, and then magnetically sorting it. Is a slag mainly composed of CaO generated when decarburizing and refining hot metal in a converter. Cast iron is mainly composed of CaO generated from a ladle containing molten steel or a tundish for continuous casting. Slag as a component.

  Using the converter type refining equipment 1 having such a configuration, the dephosphorization treatment according to the present invention is performed on the hot metal 15 as follows.

First, the hot metal 15 is charged into the furnace body 2. The dephosphorization reaction is thermodynamically advantageous at a low temperature, and if the hot metal temperature is too high, the dephosphorization reaction does not proceed. However, if the hot metal temperature is too low, hatching of the dephosphorizing refining agent 17 mainly composed of CaO does not proceed, and this also does not proceed with the dephosphorization reaction. Therefore, from the viewpoint of efficiently performing the dephosphorization reaction, the hot metal 15 to be used has a temperature converted to the initial hot metal temperature (T ₁ ) defined by the following formula (1) of 1200 to 1330 ° C. preferable. If the initial hot metal temperature (T ₁ ) satisfies the range of 1200 to 1330 ° C., a cold iron source such as iron scrap or magnetic separation scrap may be added before the dephosphorization treatment. Here, in the formula (1), T ₁ is the initial hot metal temperature (° C.), [Si] is the silicon concentration (mass%) in the hot metal, and HMR is the initial hot metal mixture ratio (hot metal mass / ( Hot metal mass + cold iron source mass added before refining))).

  On the other hand, the hot metal 15 can be processed with any composition, and desulfurization treatment or desiliconization treatment may be performed before the dephosphorization treatment. The desiliconization process is a process in which oxygen gas or iron oxide such as a mill scale is added to the hot metal 15 to mainly remove silicon from the hot metal 15. Incidentally, the main chemical components of the hot metal 15 before the dephosphorization treatment are: carbon: 3.8 to 5.0% by mass, silicon: 0.4% by mass or less, sulfur: 0.05% by mass or less, phosphorus: 0.00%. It is about 08-0.3 mass%. However, since the dephosphorization efficiency decreases when the amount of slag 16 generated in the furnace main body during the dephosphorization process increases, the desiliconization process is performed in advance in order to reduce the amount of slag 16 to be generated and increase the dephosphorization efficiency. Thus, it is preferable to reduce the silicon concentration of the hot metal 15 to about 0.2% by mass or less.

  Next, a non-oxidizing gas such as nitrogen gas or a rare gas such as Ar gas is blown into the hot metal 15 from the bottom blowing tuyere 7 as a stirring gas 18, and oxygen gas is directed from the top blowing lance 3 toward the bath surface of the hot metal 15. The dephosphorizing refining agent 17 mainly composed of CaO is supplied by spraying toward the oxygen gas spray surface of the hot metal bath surface, that is, the hot spot through the upper spray lance 3, and the hot metal 15 The dephosphorization process is started.

  As the dephosphorization refining agent 17 mainly composed of CaO, quick lime powder can be used. Alumina powder or fluorite may be added to the quicklime powder as a hatching accelerator, but in the present invention, the dephosphorizing refining agent 17 is added by spraying on the hot spot of the hot metal bath surface. Even if it exists, it fully hatches, Therefore Even if it does not use hatching promoters, such as an alumina powder and a fluorite, it can fully dephosphorize. In particular, from the viewpoint of protecting the environment by suppressing the amount of fluorine eluted from the slag 16, it is preferable not to add a fluorine-containing substance such as fluorite to the dephosphorizing refining agent 17. However, a substance in which fluorine is inevitably mixed as an impurity component may be used. If the dephosphorizing refining agent 17 is added only by projection, if the desired addition rate cannot be obtained, it may be added on top.

  In this case, before adding the dephosphorization refining agent 17 mainly composed of CaO, it is preferable to add a converter rod or a cast iron mainly composed of CaO as a dephosphorization refining agent. The converter or cast iron containing CaO as a main component is a so-called pre-melt material that has once passed through a molten state, so it is a compound composed of a plurality of oxides, has a low melting point, and quickly hatches. And has a function of promoting the hatching of the dephosphorization refining agent 17 mainly composed of CaO. Further, the converter soot contains iron oxide, and the oxygen potential of the formed slag 16 is increased, which has the effect of promoting the dephosphorization reaction.

  The hot metal 15 is stirred by the stirring gas 18 blown from the bottom blowing tuyere 7, and the dephosphorizing refining agent 17 sprayed on the bath surface of the hot metal 15 is melted at a hot spot to form a slag 16, and the hot metal 15 The dephosphorization reaction proceeds.

  At any time from the time when 30% of the planned dephosphorization time has elapsed until the time when 90% has elapsed, dephosphorization has progressed, and cold iron sources such as iron scrap and magnetically-sorted scrap are supplied to the interior of the furnace body 2. Add to the top. By adding a cold iron source, the hot metal temperature decreases. The amount of the cold iron source added is preferably determined so that the hot metal temperature at the end of dephosphorization is 1400 ° C. or lower. If the hot metal temperature at the end of dephosphorization exceeds 1400 ° C., the dephosphorization reaction is hindered and the dephosphorization treatment cannot be performed to the target phosphorus concentration, which is not preferable.

  The cold iron source added during dephosphorization is preferably as small as possible from the viewpoint of promoting dissolution, and specifically, the particle size is preferably 20 mm or less. This particle size is defined by the opening size of the sieve, and is defined as a particle size of 20 mm or less as long as it passes through a sieve having an opening size of 20 mm even if the major axis exceeds 20 mm. Further, in order to smoothly melt the cold iron source without causing a rapid temperature drop of the hot metal 15, cold iron between 30% of the dephosphorization time and 90% of the time has elapsed. It is preferable to feed the source continuously.

In the initial stage of the dephosphorization treatment, a cold iron source may be added within a range where the initial hot metal temperature (T ₁ ) converted by the above formula (1) satisfies 1200 to 1330 ° C. Since there are few, hot metal temperature rises too much and a dephosphorization reaction may be inhibited. Therefore, in that case, you may add solid oxygen sources, such as a mill scale and an iron ore, as needed. By adding a solid oxygen source, the hot metal temperature is lowered. In addition, the total amount of dephosphorizing refining agent 17 including the dephosphorizing refining agent 17 mainly composed of CaO, the converter slag, and the casting slag is changed according to the silicon concentration and the phosphorus concentration of the hot metal 15. However, if the basicity (CaO / SiO ₂ ) of the slag 16 is in the range of 2 or more, it is sufficient that the maximum is about 40 kg per ton of hot metal. The lance height is not particularly limited, and may be set in consideration of the amount of slag 16 generated.

  As described above, in the hot metal dephosphorization processing method according to the present invention, the cold iron source such as iron scrap and magnetic separation scrap added before the dephosphorization process is limited, and the hot iron temperature mainly increases the hot metal temperature. Since it is introduced after the middle stage of the dephosphorization refining, there is no excessive decrease in the hot metal temperature in the initial stage of the dephosphorization refining. The dephosphorization reaction can proceed with high efficiency from the beginning. This makes it possible to increase the amount of cold iron source used without extending the dephosphorization processing time, and achieve resource saving, energy saving, productivity improvement, and the like.

  The dephosphorization process was implemented with the converter type refining equipment shown in FIG. At that time, when the cold iron source is charged all at once before the start of the dephosphorization refining (comparative example) and when the continuous depletion time is 30% until the time when 90% elapses. It implemented about 2 levels of (invention example). The amount of cold iron source added, the amount of dephosphorizing refining agent added, the amount of oxygen gas supplied, the composition of the hot metal used, etc. were the same in the present invention example and the comparative example.

  As a result, in the inventive example, the average value of the phosphorus concentration in the hot metal at the end of the dephosphorization was 0.020% by mass, and the standard deviation (σ) was 0.004% by mass. On the other hand, in the comparative example, the average value of the phosphorus concentration in the hot metal at the end of the dephosphorization refining is 0.025% by mass, and the standard deviation (σ) is 0.007% by mass. It was confirmed that the dephosphorization treatment could be carried out with

It is a schematic sectional drawing which shows one example of the converter type refining equipment used when implementing the dephosphorization processing method of the hot metal which concerns on this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Converter type refining equipment 2 Furnace main body 3 Top blowing lance 4 Iron skin 5 Refractory 6 Outlet 7 Bottom blowing tuyere 8 Gas introduction pipe 9 Oxygen gas piping 10 Nitrogen gas piping 11 Dispenser 12 Flow control valve 13 Flow control valve 14 Flow control valve 15 Hot metal 16 Slag 17 Refining agent for dephosphorization 18 Gas for stirring 19 Transfer piping

Claims (3)

A dephosphorizing refining agent mainly composed of CaO is added to the hot metal contained in the converter type refining vessel, and the dephosphorizing refining agent added by blowing up oxygen gas is hatched to form slag. In the hot metal dephosphorization method, a hot metal having an initial hot metal temperature (T ₁ ) before dephosphorization defined by the following formula ( ₁ ) of 1200 to 1330 ° C. is used: The hot metal temperature at the end of the dephosphorization refining is 1400 ° C. or less by adding a cold iron source in the refining vessel at any time from the time when 30% of the dephosphorization refining time has elapsed to the time when 90% has elapsed. A hot metal dephosphorization method, characterized by adjusting to
T ₁ (° C) = [Hot metal temperature (° C) + [Si] x 300] x HMR (1)
However, in the formula (1), T ₁ is the initial hot metal temperature (° C.) before the dephosphorization treatment, [Si] is the silicon concentration (mass%) in the hot metal, and HMR is the initial hot metal mixture ratio ( Hot metal mass / (Mold iron mass + Cold iron source mass added before refining)).   2. The hot metal dephosphorization method according to claim 1, wherein the cold iron source is continuously added from the time when 30% of the dephosphorization time has elapsed to the time when 90% has elapsed. The hot metal according to claim 1 or 2, wherein the particle size of the cold iron source added from the time when 30% of the dephosphorizing time has elapsed until the time when 90% has elapsed is 20mm or less. Dephosphorization method.

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