JP6330710B2 - Hot metal dephosphorization and decarburization methods - Google Patents

Description

  The present invention relates to a hot metal dephosphorization and decarburization method, and more particularly to a dephosphorization and decarburization method in which high-efficiency dephosphorization up to a low phosphorus concentration is performed under a low slag generation amount.

In recent years, a hot metal pretreatment method in which dephosphorization treatment is performed at the hot metal stage instead of the conventional converter method has been widely used. That is, the dephosphorization reaction proceeds more thermodynamically as the refining temperature is lower, and the dephosphorization treatment can be performed with a smaller amount of the refining agent.
In general, in the hot metal preliminary treatment, first, a solid oxygen source such as iron oxide is added to the hot metal for desiliconization treatment. After removing slag generated by this desiliconization treatment, a refining agent (medium solvent) is added. Dephosphorization is performed. Usually, a CaO-based refining agent such as quicklime is used as the dephosphorizing refining agent, and a solid oxygen source (such as iron oxide) or gaseous oxygen is used as the oxygen source. Moreover, a torpedo car, a ladle (charging pot), a converter type container, etc. are used as a processing container.

Conventionally, in hot metal dephosphorization, CaF ₂ (fluorite) has been widely added to promote hatching of a CaO-based solvent. However, in recent years, there is a tendency that regulatory standards of fluorine elution amount from the slag from the viewpoint of environmental protection is enhanced, Thus, operation with reduced use amount of CaF _2, or operation that does not use CaF ₂ is sought A method of adding TiO ₂ (titanium oxide) or Al ₂ O ₃ (alumina) instead of CaF ₂ has been proposed (for example, Patent Documents 1 and 2).

  Further, in the hot metal pretreatment method, since the hot metal dephosphorization process and the decarburization process are performed in separate processing containers, the hot metal temperature decreases every time the hot metal is supplied to the processing container. Because of this temperature drop, the amount of iron scrap in the refining process for producing molten steel from hot metal is reduced. On the other hand, as one method of increasing the amount of iron scrap even in the hot metal pretreatment method, the same converter type vessel is used, and the dephosphorization treatment and the decarburization treatment are performed in the middle of these processes. There has been proposed a steel making method that is performed continuously with a gap between them (see, for example, Patent Document 3).

JP 2008-63645 A JP 2008-63646 A Japanese Patent Laid-Open No. 4-72007

However, the above prior art has the following problems.
In other words, the techniques described in Patent Documents 1 and ₂ add about 10% of TiO ₂ or Al ₂ O ₃ , so that the use efficiency of lime is improved, but the amount of slag to be generated is increased.
The technology described in Patent Document 3 can improve the utilization efficiency of lime and reduce the amount of slag by reusing the slag used in the decarburization process in the desiliconization and dephosphorization processes. The problem was that the amount of phosphorus was limited and it was difficult to melt ultra-low phosphorus steel.

  The present invention has been made in view of the above circumstances, and an object thereof is to propose a dephosphorization and decarburization method capable of efficiently performing dephosphorization to a low phosphorus concentration under a low slag generation amount. To do.

The inventors diligently devised ways to increase the efficiency of dephosphorization in a technique that can improve the utilization efficiency of lime and reduce the amount of slag by reusing the slag used in the decarburization process and dephosphorization process. As a result of investigation, it was found that it is extremely effective to add dicalcium silicate (2CaO · SiO ₂ , hereinafter also referred to as C ₂ S) when reusing slag, and the present invention has been completed.

That is, the gist configuration of the present invention is as follows.
1. Step 1 of charging the hot metal into a converter, supplying oxygen gas to the hot metal and supplying a lime-based solvent to perform dephosphorization and decarburization of the hot metal,
A step 2 of tapping the molten steel after the dephosphorization and decarburization treatment, and leaving at least a part of the slag generated in the step 1 in the converter;
The hot metal is newly charged into the converter in which the slag remains, and then oxygen gas is supplied to the hot metal, and at least dicalcium silicate (2CaO · SiO ₂ ) is added to dephosphorize the hot metal and Step 3 for performing decarburization treatment;
Of dephosphorization and decarburization of hot metal having metal

2. The method for dephosphorizing and decarburizing hot metal in the converter according to 1 above, wherein the dicalcium silicate is added in an amount defined by the following formula (1).
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3. 3. The hot metal dephosphorization and decarburization method according to 1 or 2 above, wherein, in the step 2, in addition to the dicalcium silicate, a lime-based solvent that satisfies the weight of CaO calculated by the following equation (5) is added.
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なお、前記各式における下付き添え字ｉは前記繰り返しの回数を示す。 4). The method further includes the step of repeating the step 3, and adding the amount of dicalcium silicate defined by the following formula (6) for each repetition, and the amount of slag defined by the following formula (9) for each repetition 4. The method for dephosphorizing and decarburizing hot metal as described in any one of 1 to 3 above, wherein slag is retained.
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In addition, the subscript i in each said formula shows the frequency | count of the said repetition.

According to the present invention, by efficiently concentrating phosphorus in solid C ₂ S, the amount of slag per treatment can be greatly reduced, and the slag can be reused at a high temperature. Compared to the new conventional method of adding flux, a thermal margin can be obtained. In addition, since the dephosphorization is performed by utilizing the undehydrated lime in the slag, there is an effect that the undehydrated lime in the slag after the treatment is reduced and the treatment cost at the time of recycling is reduced.

It is a figure which shows the processing flow of this invention. Basicity (C / S) and% f. It is a graph which shows the relationship with CaO. 4 is a graph showing the relationship between the amount of C ₂ S added and the amount of dephosphorization at each basicity (C / S). In the slag f. It is a graph which shows the relationship between the amount of CaO (kg / t) and the required amount of C ₂ S addition. It is a graph which shows the relationship between CaO addition amount and dephosphorization amount. It is a graph which shows the relationship between the amount of slag and the amount of dephosphorization.

Hereinafter, the present invention will be specifically described.
First, the hot metal used in the present invention is a hot metal produced in a blast furnace, and this hot metal is received by a hot metal transfer container such as a hot metal ladle or a topped car and transferred to a converter for dephosphorization and decarburization. Since hot metal dephosphorization is effective at low temperatures, it is common to perform preliminary dephosphorization prior to dephosphorization and decarburization in a converter. In the case of performing this preliminary dephosphorization treatment, in order to efficiently perform the dephosphorization treatment with a small amount of lime-based solvent in decarburization and refining in the converter, the silicon content of the hot metal is, for example, 0.10 mass% or less, It is desirable to reduce it to 0.05 mass% or less, and to reduce the phosphorus content of hot metal to 0.08 mass%, for example, and desirably 0.05 mass% or less.
Similarly, in order to efficiently perform the dephosphorization treatment with a small amount of lime-based medium solvent used in the preliminary dephosphorization treatment, the desiliconization treatment is performed prior to the preliminary dephosphorization treatment, and the silicon content of the hot metal is, for example, 0.20. It is preferable to reduce the mass to below 0.10 mass%, preferably below 0.10 mass%. Note that when preliminary dephosphorization treatment and / or desiliconization treatment is performed, the slag produced by these treatments is dephosphorized and converted in the converter. Discharge before decarburization.

(Process 1)
Next, as shown in FIG. 1, the hot metal 1 subjected to the preliminary dephosphorization treatment is charged into the converter 2 as necessary, and an oxygen-containing gas is supplied from the top blowing lance 3, Is dephosphorized and decarburized by producing slag 4 having a viscosity of 3.0 or more, more preferably 4.0 or more. Specifically, the basicity of the slag to be generated is controlled within the above range by adjusting the addition amount and / or composition of the lime-based medium solvent. In addition, when the hot metal to be charged is sufficiently desiliconized (0.10 mass% or less) in the preliminary treatment, when the lime-based solvent is added, the molten steel is oxidized to produce a CaO-FeO-based melt, Since the yield of molten steel decreases, it is preferable to generate CaO—SiO ₂ slag of 5.0 kg / t or more, desirably 10.0 kg / t or more. Specifically, the slag amount may be adjusted by adding a SiO ₂ source such as silica stone together with the lime-based medium solvent.

In the slag after the above dephosphorization and decarburization treatment, about 40 mass% of CaO is usually contained, and about 5 mass% or less of that remains in the slag while not yet being hatched. When such undegraded CaO remains, when recycling slag after treatment to roadbed materials, etc.,
CaO + H ₂ O═Ca (OH) ₂
In order to cause the hydration expansion represented by this reaction, it is necessary to perform watering treatment in advance, and there is a problem that the processing cost increases.

By the way, phosphorus in hot metal reacts with lime,
CaO + 2 [P] + 5 / 2O ₂ = 3CaO · P ₂ O ₅
It is known that dephosphorization proceeds by this reaction. Here, [P] represents phosphorus in the hot metal. In the actual process, CaO is mainly present as CaO—SiO ₂ —FeO-based slag, and phosphorus is present as 2CaO · SiO ₂ -3CaO · P ₂ O ₅ solid solution (hereinafter referred to as C ₂ S—C ₃ P solid solution). .

(Process 2)
In the present invention, since such undehydrated CaO remains, the slag remains in the converter and is reused.

(Process 3)
Then, newly charged with hot metal 1 into said transfer furnace 2, by adding C ₂ S, was intended to be formed of C ₂ S-C ₃ P solid solution described above. That is, the target dephosphorization and decarburization processes can be performed with a slight amount of dephosphorization agent while effectively utilizing undenitrated CaO.

Here, as C ₂ S to be added, any substance containing a C ₂ S phase, such as a product obtained by baking a mixture of quicklime and silica, or a product obtained by pulverizing slag produced in a steelmaking process, may be used. It is available without. It is preferable content in dephosphorization agent C ₂ S is not less than 10 mass%. This is because when the C ₂ S content is low, the ratio of the remaining components (Al ₂ O ₃ , MgO, etc.) increases, and the amount of slag increases when the required amount of C ₂ S is added, and slag jetting during processing This is because there are concerns about operational troubles. Moreover, in order to keep the basicity of slag high, it may be necessary to add extra lime sources such as quicklime. In order to shorten the treatment time when C ₂ S is added, it is necessary to quickly disperse the added C ₂ S in the slag, and it is preferable to use C ₂ S powder. The particle diameter of the C ₂ S powder is more preferably 1 mm or less.

C ₂ S added in the dephosphorization process by reusing the slag is preferably added in an amount W _C2S defined by the following formula (1).
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The above formula (1) defines the amount of C ₂ S added (W _C2S ) based on the slag weight W _slag before adding C ₂ S in the reuse of slag.
Hereinafter, a method for defining the expression (1) will be described.
First, the basicity (C / S) of slag before C ₂ S addition and% f. As shown by the relationship with CaO, it can be seen that the two are in a certain relationship. Next, FIG. 3 is a graph showing the relationship between the C ₂ S addition amount and the dephosphorization amount with the basicity (C / S) as a parameter. That is, the results of investigating the conditions for obtaining the target dephosphorization amount ΔP by changing the C ₂ S addition amount at each basicity level (C / S: 2.5, 3.0, 3.5, 4.0) are shown. From the figure, it can be seen that there is an optimum amount of C ₂ S added at each basicity level, and ΔP is saturated even if C ₂ S is added excessively.
The saturation point in FIG. 3 and the basicity (C / S) in FIG. Based on the relationship with CaO, f. FIG. 4 shows the results of investigating the relationship between the CaO amount (kg / t) and the required C ₂ S addition amount. From the figure, it can be seen that by adding the amount of C ₂ S in the reuse of slag within a range that satisfies the above formula (1), an appropriate amount of C ₂ S can be added without any shortage. .

Further, in the step 2, in the case where the left side> the right side in the formula (1), C ₂ S becomes excessive and is wasted. Therefore, it is preferable to add a lime-based medium solvent satisfying the following formula (5).
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That is, in order to consume excess C ₂ S and perform dephosphorization / decarburization in step 3, a CaO amount lime-based medium solvent calculated from the equation (5) is added. Further, W _lime may be added in excess from the formula (5), but in that case f. C ₂ S is preferably added to regenerate CaO.

Furthermore, as shown by the chain line arrow in FIG. 1 described above, the dephosphorization and decarburization treatment can be continued by repeating the step 3. At that time, it is preferable to add an amount of dicalcium silicate defined by the following formula (6) for each repetition and to leave an amount of slag defined by the following formula (9) for each repetition.
Record

This is because, as described above, by adding C ₂ S, it is possible to effectively utilize the undehydrated lime in the slag and to perform high-efficiency dephosphorization up to a low phosphorus concentration with a small amount of slag generated. It becomes. However, if the amount of slag in the container is increased by repeatedly using slag, slag ejection may occur from the container, which may cause operational trouble. For this reason, it is preferable that the amount of slag left in the furnace is an amount defined by the equation (9).

As described above, according to the present invention, by adding a C ₂ S in the slag after the dephosphorization, decarburization refining, can be fixed phosphorus in the molten iron as C ₂ S-C ₃ P solid solution In addition, phosphorus can be more efficiently concentrated in the slag. As a result, it is possible to melt a steel grade having a phosphorus concentration of 0.01 mass% or less simply by adding a small amount of solid C ₂ S and a lime-based solvent for maintaining slag basicity. It is also possible to greatly reduce the amount of slag.

Furthermore, by leaving at least a part of the slag after dephosphorization and decarburization and reusing the slag in the converter, a thermal margin can be obtained compared to adding new flux, and the hot metal temperature can be increased. There is also a margin for reducing the amount of scrap and charging, so that an advantage of increasing the amount of scrap can be obtained.
In addition, the phosphorus concentration of the slag after a process is higher than before, and phosphorus recovery from slag can be efficiently performed regardless of a wet method or a dry method. In addition, undecalcified CaO remaining in slag after conventional decarburization refining is used to form a C ₂ S—C ₃ P solid solution, and after dephosphorization / decarburization treatment to which the present invention is applied. This slag does not cause hydration expansion. For this reason, it becomes possible to use the slag after a process for a roadbed material directly.

Preliminary dephosphorization of the hot metal and decarburization refining were performed using two top-bottom blowing converters with a furnace capacity of 2.5 tons. The hot metal having the composition and temperature shown in Table 1 was melted (preliminary treatment) in the first top bottom blowing converter, and the molten iron after the preliminary treatment was charged into the second top bottom blowing converter. Dephosphorization and decarburization treatments were performed to obtain post-treatment molten steel shown in Table 1.
That is, in the second top bottom blowing converter, argon gas was blown into the hot metal as a stirring gas from the bottom blowing tuyere while blowing the oxygen gas for refining from the top blowing lance toward the hot metal surface. The amount of iron scrap charged was adjusted so that the dephosphorization / decarburization end temperature ranged from 1645 to 1652 ° C. For hot metal charged in the second top-bottom blown converter, quick lime (CaO) and silica (SiO2) so that the calculated slag after treatment is 22.5 to 25.4 kg / t and the calculated basicity is 2.5 to 4.0. _{After 2} ) was added and dephosphorization and decarburization were performed, the molten steel was poured into a ladle and treated to leave slag in the converter.

Next, after the molten iron having the composition and temperature shown in Table 2 is newly charged in the converter with the slag remaining, quick lime (CaO) and C ₂ S are added to perform dephosphorization and decarburization refining. Then, the molten steel was poured out into the ladle and the slag was discharged into the pan. Here, the calculated slag amount was obtained from the above-described equation (4). Further, C ₂ S used was obtained by mixing quick lime and quartzite at a weight ratio of 112: 60 and firing at 1300 ° C. using a rotary kiln.

As is apparent from Table 2, all of the inventive examples to which C ₂ S is added in the slag reuse reduce the amount of slag produced and increase the amount of dephosphorization as compared with the comparative example.

Inventive Examples 33 to 36 were processed so that the basicity was 3.0 as the 1st channel treatment, and quick lime was added simultaneously with the addition of C ₂ S at the _2nd channel. The f.CaO in the slag produced at the first channel is about 0.84 kg / t, and the case where only C ₂ S is added corresponds to Invention Example 30. As is apparent from FIG. 5, when the amount of C ₂ S added is constant at 4.0 kg / t, ΔP increases by increasing the amount of quicklime added simultaneously. This is because, as shown in FIG. 3, to add conditions to C ₂ S 4.0kg / t of basicity 3.0 is excessive C ₂ S, consider the added lime is that it due to a reaction with an excess of C ₂ S It is done.

  Furthermore, it shows in Table 3 about the result of having repeated the above-mentioned process. Although the effect tends to diminish as the number of times passes, it can be seen that the amount of dephosphorization is secured as compared with the case of simply reusing slag.

Claims (4)

Step 1 of charging the hot metal into a converter, supplying oxygen gas to the hot metal and supplying a lime-based solvent to perform dephosphorization and decarburization of the hot metal,
A step 2 of tapping the molten steel after the dephosphorization and decarburization treatment, and leaving at least a part of the slag generated in the step 1 in the converter;
The molten iron is newly charged into the converter in which the slag remains, and then oxygen gas is supplied to the molten iron, and at least dicalcium silicate (2CaO · SiO ₂ ) is added to remove the molten iron. Step 3 for performing decarburization treatment;
A method for dephosphorizing and decarburizing hot metal having The method for dephosphorization and decarburization of hot metal in a converter according to claim 1, wherein the dicalcium silicate is added in an amount defined by the following formula (1).
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3. The hot metal dephosphorization and decarburization method according to claim 1, wherein in step 2, in addition to dicalcium silicate, a lime-based solvent that satisfies the weight of CaO calculated by the following equation (5) is added. .
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The method further includes the step of repeating the step 3, and adding the amount of dicalcium silicate defined by the following formula (6) for each repetition, and the amount of slag defined by the following formula (9) for each repetition The method for dephosphorizing and decarburizing hot metal according to any one of claims 1 to 3, wherein:
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