Patent Application
20240158886
The present invention relates to a method for producing iron ore pellets.
As a blast furnace operation, a method is well-known in which pig iron is produced by: alternately stacking, in a blast furnace, a first layer containing an iron ore material, and a second layer containing coke; and injecting an auxiliary reductant into the blast furnace from a tuyere and melting the iron ore material by using resulting hot blasts. In this method for producing pig iron, the iron ore material, being supplied as iron ore pellets, is reduced, whereby the pig iron is produced. At this time, the coke functions as a reduction agent and serves as a spacer to secure gas permeability.
The iron ore pellets need to have high reducibility in order to improve production efficiency of pig iron. As iron ore pellets having improved reducibility, for example, iron ore pellets obtained by adding dolomite to make a CaO/SiO2 mass ratio greater than or equal to 0.8 and a MgO/SiO2 mass ratio greater than or equal to 0.4 are known (see Japanese Unexamined Patent Application Publication No. H1-136936). The aforementioned publication further discloses that increasing porosity of the iron ore pellets can improve reducibility.
In light of a recent increase in awareness of the environmental problems, a reduction in emission of CO2 as the greenhouse gas, specifically an operation with a low reduction agent ratio, is required also in a blast furnace operation. In this case, since pulverization of the iron ore pellets in the blast furnace and the like leads to lowered gas permeability, a large amount of coke as a spacer for ensuring gas permeability needs to be charged. An increased charged rate of coke as a reduction agent increases the reduction agent ratio, whereby an operation with a low reduction agent ratio is difficult. Therefore, in order to carry out an operation with a low reduction agent ratio, the iron ore pellets need to have a high crushing strength so as not to be pulverized.
However, adding dolomite tends to lower the crushing strength. In addition, increasing the porosity of the iron ore pellets necessarily lowers the crushing strength.
The present invention was made in view of the foregoing circumstances, and an objective thereof is to provide a method for producing iron ore pellets superior in reducibility and high in crushing strength.
The present inventors have thoroughly investigated iron ore pellets obtained by adding dolomite to increase reducibility, and found that adding dolomite treated to be present in a miniaturized state in a pellet structure prior to firing increases crushing strength. Although an exact reason is not clear, the present inventors infer that, by subjecting dolomite to a predetermined treatment, MgO derived from the dolomite is present in a miniaturized state in the iron ore pellets, whereby an effect of increasing a bonding strength of the pellet structure of the iron ore pellets is produced during firing. In other words, the bonding strength of the pellet structure is considered to be increased due to the fact that: MgO being miniaturized increases reactivity of MgO and facilitates generation of a magnesioferrite compound, thus contributing to bonding of the pellet structure; and/or MgO having a low bonding strength that may be an origin of fracture of the pellet is miniaturized and less likely to be the origin of fracture.
In other words, according to an aspect of the present invention, a method for producing iron ore pellets used for operation of a blast furnace and in which a CaO/SiO2 mass ratio is greater than or equal to 0.8 and a MgO/SiO2 mass ratio is greater than or equal to 0.4 includes: balling green pellets by adding, to an iron ore material and dolomite, water for use in the balling; and firing the green pellets, in which the dolomite has a characteristic of being present in a miniaturized state in a structure of the green pellets.
The method for producing iron ore pellets enables increasing crushing strength of the iron ore pellets to be produced, by adding dolomite that is present in a miniaturized state in a structure of the green pellets prior to firing and produces an effect of increasing the bonding strength of the pellet structure of the iron ore pellets. In addition, in the iron ore pellets produced by the method for producing iron ore pellets, a CaO/SiO2 mass ratio is greater than or equal to 0.8 and a MgO/SiO2 mass ratio is greater than or equal to 0.4, resulting in high reducibility.
It is preferred that the method for producing iron ore pellets further includes preparing the dolomite, in which in the preparing, the dolomite is pulverized such that a Blaine specific surface area is greater than or equal to 4,000 cm2/g. Due to the Blaine specific surface area of the dolomite being greater than or equal to the lower limit, the dolomite is miniaturized and integrated into the pellet structure. As a result, reactivity of dolomite can be increased, and MgO can be inhibited from functioning as an origin of fracture in the iron ore pellets to be produced. Therefore, the bonding strength of the pellet structure of the iron ore pellets is increased, whereby the crushing strength of the iron ore pellets can be increased. As used herein, a “Blaine specific surface area” means a value obtained by measurement in accordance with JIS-R-5201:2015, and, in a case in which a target object is composed of a plurality of powders, indicates a minimum value for an individual powder.
It is preferred that the method for producing iron ore pellets further includes preparing the dolomite, wherein the dolomite is calcined at a temperature greater than or equal to 900° C. in the preparing. As used herein, “calcination” means a heat treatment process of heating a solid such as ore to cause thermal decomposition and phase transition, and to remove volatile components. Dolomite is a carbonate mineral and represented by CaMg(CO3)2. When dolomite is calcined, the following reaction takes place
CaCO3->CaO+CO2,MgCO3->MgO+CO2
and dolomite is thermally decomposed. At a phase of balling, water is added to MgO generated by the calcination, resulting in a transformation into Mg(OH)2 and miniaturization (dolomite having a large grain size is reduced). As a result, reactivity of dolomite can be increased, and MgO which is generated in the firing and can function as an origin of fracture in the iron ore pellets to be produced can be miniaturized. Therefore, the bonding strength of the pellet structure of the iron ore pellets to be produced is increased, whereby the crushing strength of the iron ore pellets can be increased.
The firing temperature in the firing preferably higher than or equal to 1,250° C. Due to the firing temperature in the firing being higher than or equal to the aforementioned lower limit, the crushing strength can further be increased.
As explained in the foregoing, by employing the method for producing iron ore pellets according to the present invention, iron ore pellets superior in reducibility and having high crushing strength can be produced.
Hereinafter, the method for producing pig iron according to each embodiment of the present invention will be described.
The method for producing iron ore pellets illustrated in
The iron ore pellets 1 are obtained by balling and firing finely pulverized ore to form agglomerated ore having a great strength. Regarding production of the iron ore pellets 1, it is known that adding a CaO-containing compound such as limestone to an iron ore material to increase a CaO/SiO2 mass ratio in the iron ore pellets 1 improves reducibility of the iron ore pellets 1 (see Patent Document 1). On the basis of this finding, the present method for producing iron ore pellets produces the iron ore pellets 1 having the CaO/SiO2 mass ratio of greater than or equal to 0.8.
In a case in which the raw materials are iron ore (iron oxide) and limestone (CaO-containing compound), a calcium ferrite compound is generated by a solid phase reaction between CaO generated by the thermal decomposition and iron oxide in the firing, and is simultaneously bound through solid phase diffusion bonding at an interface thereof. Since the bonding is local, fine pores which were present prior to the firing are retained even after the firing, whereby the iron ore pellets 1 are porous bodies in which fine pores are present relatively uniformly.
During the blast furnace operation, a reducing gas enters the fine pores diffusively, whereby a reduction reaction proceeds from an outer surface to an inner portion of the iron ore pellets 1. Due to removal of oxygen from the iron oxide by the reduction reaction, the existing fine pores are enlarged and new fine pores are generated, while metallic iron is generated. In a process of shrinkage of an external shape of the iron ore pellets 1 due to aggregation of the metallic iron, the fine pores start to decrease. As a result, diffusion of the reduction gas into the iron ore pellets 1 is suppressed, whereby the reduction is likely to stagnate.
For suppressing this stagnation of the reduction, addition of a high-melting point component which suppresses loss of the fine pores during an aggregation process of the metallic iron is effective. It is known that particularly adding dolomite as a source of MgO, which is the high-melting point component, to increase a MgO/SiO2 mass ratio in the iron ore pellets 1 enables obtaining a powerful effect of suppressing stagnation of the reduction (see Patent Document 1). On the basis of this finding, in the present method for producing iron ore pellets, the iron ore pellets 1 are produced having the MgO/SiO2 mass ratio of greater than or equal to 0.4.
It is preferred that the iron ore pellets to be produced are self-fluxing. Due to the iron ore pellets 1 being self-fluxing, melting down of reduced iron is likely to be accelerated. Note that the self-fluxing property of the iron ore pellets 1 is determined by an auxiliary material and/or the like.
In the preparing step S1, dolomite is prepared. In the present method for producing iron ore pellets, the dolomite has a characteristic of being present in a miniaturized state in a structure of green pellets P to be balled in the balling step S2 described later. In the preparing step S1, this characteristic is imparted to the dolomite. Specifically, in the preparing step S1, the dolomite is pulverized such that a Blaine specific surface area is greater than or equal to a predetermined value. Note that the pulverization can be carried out by using a known pulverizer.
The predetermined value is preferably 4,000 cm2/g, and more preferably 6,000 cm2/g. Increasing the specific surface area is considered to be substantially the same as miniaturizing the dolomite. Due to the miniaturization, reactivity of dolomite can be increased, and MgO can be inhibited from functioning as an origin of fracture in the iron ore pellets 1 to be produced. Therefore, the bonding strength of the pellet structure of the iron ore pellets 1 to be produced is increased, whereby the crushing strength of the iron ore pellets 1 can be increased. Note that an upper limit of the Blaine specific surface area of the pulverized dolomite is not particularly limited, but in view of production cost and the like, the Blaine specific surface area of the pulverized dolomite is less than or equal to 10,000 cm2/g.
A lower limit of a percentage of particles having a grain size of less than or equal to m in the pulverized dolomite is preferably 35% by volume, more preferably 45% by volume, and further preferably 55% by volume. The percentage of particles having a grain size of less than or equal to 20 μm being greater than or equal to the lower limit facilitates an increase in the crushing strength of the iron ore pellets 1. Note that the “percentage of particles having a grain size of less than or equal to 20 μm” indicates a value obtained from a grain size distribution measured by a grain size distribution measurement apparatus (Microtrac).
An upper limit of a D50 grain size of the pulverized dolomite is preferably 50 m and more preferably 20 m. The D50 grain size of the dolomite being less than or equal to the upper limit facilitates an increase in the crushing strength of the iron ore pellets 1. Note that the “D50 grain size” indicates a value obtained from a grain size distribution measured by a grain size distribution measurement apparatus (Microtrac).
In the balling step S2, green pellets P are balled by adding water for use in the balling to an iron ore material and the dolomite. As described above, an auxiliary material such as limestone may be added to obtain the CaO/SiO2 mass ratio of greater than or equal to 0.8. The MgO/SiO2 mass ratio can be adjusted mainly by the dolomite.
Specifically, in the balling step S2, the water is added to the iron ore material and the dolomite, and then this water-containing mixture (the iron ore material and the dolomite containing the water) is charged into the pan pelletizer 3, serving as the pelletizer, and rolled to produce the green pellets P, having a ball shape.
The iron ore material is a main material of the iron ore pellets 1, and composed of powder of the iron ore (for example, powder of which at least 90% by mass of the total has a grain size of less than or equal to 0.5 mm). Although surface characteristics of the iron ore vary greatly depending upon a mining region and a pulverizing/transporting method, the surface characteristics of the iron ore are not particularly limited in the present method for producing iron ore pellets.
The water constitutes bridges between particles of the iron ore material. Strength of the green pellets P balled in the balling step S2 is maintained due to an adhesion force acting between the particles, resulting from this bridging. In other words, a bond between the particles is expressed by means of surface tension of the water between the particles, and the adhesion force between the particles is ensured by a value obtained by multiplying the surface tension by the number of points of contact between the particles.
In the firing step S3, the green pellets P are fired. In the firing step S3, the traveling grate furnace 4 and the kiln 5 are used.
As shown in
The traveling grate 41 is configured to be endless, and the green pellets P placed on this traveling grate 41 can be transferred to the drying chamber 42, the dehydrating chamber 43, and the preheating chamber 44, in this order.
In the drying chamber 42, the dehydrating chamber 43, and the preheating chamber 44, the green pellets P are subjected to: drying by a heating gas G1; dehydrating; and preheating, whereby preheated pellets H are obtained having strength, imparted to the green pellets P, sufficient to resist the rotation in the kiln 5.
Specifically, the following procedure is followed. First, in the drying chamber 42, the green pellets P are dried at an atmospheric temperature of about 250° C. Next, in the dehydrating chamber 43, the green pellets P after the drying are heated to about 450° C. in order to mainly decompose and remove combined water in the iron ore. Furthermore, in the preheating chamber 44, the green pellets P are heated to about 1,100° C., whereby carbonate contained in limestone, dolomite, and/or the like is degraded to remove carbon dioxide, and magnetite in the iron ore is oxidized. Accordingly, the preheated pellets H are obtained.
As shown in
The kiln 5 is directly connected to the traveling grate furnace 4, and is a rotary furnace having a sloped cylindrical shape. The kiln 5 fires the preheated pellets H which are discharged from the preheating chamber 44 of the traveling grate furnace 4. Specifically, the preheated pellets H are fired by combustion with a kiln burner (not shown in the figure) provided on an outlet side of the kiln 5. Accordingly, high-temperature iron ore pellets 1 are obtained.
A lower limit of the firing temperature for firing the preheated pellets H is preferably 1,250° C., and more preferably 1,300° C. Due to the firing temperature being higher than or equal to the aforementioned lower limit, the crushing strength can further be increased. On the other hand, the upper limit of the firing temperature is not particularly limited, and may be, for example, 1,500° C. When the firing temperature is higher than the upper limit, the effect of increasing the crushing temperature tends to be saturated and the effect may be insufficient with respect to the increase in the production cost. In addition, in light of reduction in a cohesion amount of the iron ore pellets 1 according to a rise in temperature, the upper limit is more preferably 1400° C.
In the kiln 5, as air for combustion, an atmosphere serving as a cooling gas G3 used in the annular cooler 6 is used. Furthermore, the high-temperature combustion exhaust gas G2 used for firing the preheated pellets H is sent to the preheating chamber 44 as the heating gas G1.
In the cooling step S4, the high-temperature iron ore pellets 1 obtained in the firing step S3 are cooled. In the cooling step S4, the annular cooler 6 is used. The iron ore pellets 1 cooled in the cooling step S4 are accumulated and used in the blast furnace operation.
In the annular cooler 6, the iron ore pellets 1 can be cooled by blowing the atmosphere serving as the cooling gas G3 by using a blowing apparatus 61, while transferring the high-temperature iron ore pellets 1 discharged from the kiln 5.
It is to be noted that the cooling gas G3, which was used in the annular cooler 6, resulting in an increase in temperature, is sent to the kiln 5 and used as the air for combustion.
In the method for producing iron ore pellets, dolomite, being present in a miniaturized state in a structure of the iron ore pellets 1 and producing an effect of increasing the bonding strength of the pellet structure of the iron ore pellets 1, is added. Specifically, due to the Blaine specific surface area of the dolomite being greater than or equal to 4,000 cm2/g, the dolomite is miniaturized and integrated into the pellet structure. As a result, reactivity of dolomite can be increased, and MgO can be inhibited from functioning as an origin of fracture in the iron ore pellets 1 to be produced. Therefore, the bonding strength of the pellet structure of the iron ore pellets 1 is increased, whereby the crushing strength of the iron ore pellets 1 can be increased. In addition, in the iron ore pellets 1 produced by the method for producing iron ore pellets, a CaO/SiO2 mass ratio is greater than or equal to 0.8 and a MgO/SiO2 mass ratio is greater than or equal to 0.4, resulting in high reducibility.
According to another embodiment of the present invention, a method for producing iron ore pellets used for operation of a blast furnace and in which a CaO/SiO2 mass ratio is greater than or equal to 0.8 and a MgO/SiO2 mass ratio is greater than or equal to 0.4, includes, as illustrated in
In the method for producing iron ore pellets, the steps except for the preparing step S1 are the same as the corresponding steps in the method for producing iron ore pellets according to the first embodiment. Hereinafter, the preparing step S1 is described and description for the other steps is omitted.
In the preparing step S1 in the method for producing iron ore pellets, the dolomite is calcined at a temperature greater than or equal to a predetermined value. The present inventors have found that this treatment imparts to the dolomite a characteristic of being present in a miniaturized state in a structure of the green pellets, whereby the crushing strength of the iron ore pellets to be produced can be increased.
The predetermined value is preferably 900° C., and more preferably 1,100° C. Note that an upper limit of a calcination temperature is not particularly limited, but in view of production cost and the like, the calcination temperature is less than or equal to 1,500° C.
The effect of enabling an increase in the crushing strength of the iron ore pellets produced by the calcination is discussed. Dolomite is a carbonate mineral and represented by CaMg(CO3)2. When dolomite is calcined, the following reaction takes place
CaCO3->CaO+CO2,MgCO3->MgO+CO2
and dolomite is thermally decomposed. At a phase of the balling step S3, water is added to MgO generated by the calcination, resulting in the following hydration reaction
MgO+H2O->Mg(OH)
to give magnesium hydroxide.
The present inventors found that miniaturization of the dolomite proceeds in the calcined dolomite due to the hydration reaction.
A lower limit of a treatment time of the calcination is preferably 20 minutes, more preferably 50 minutes, and still more preferably 100 minutes. Meanwhile, the upper limit of the treatment time of the calcination is preferably 200 minutes and more preferably 150 minutes. When the treatment time of the calcination is less than the lower limit, thermal decomposition may not sufficiently proceed and the improvement in the crushing strength of the iron ore pellets may be insufficient. To the contrary, when the treatment time of the calcination is greater than the upper limit, the effect of increasing the crushing temperature tends to be saturated and the effect may be insufficient with respect to the increase in the production cost.
A lower limit of a percentage of particles having a grain size of less than or equal to 20 μm in the dolomite after the hydration reaction (after the balling step S3) is preferably 45% by volume, and more preferably 55% by volume. The percentage of particles having a grain size of less than or equal to 20 m being greater than or equal to the lower limit facilitates an increase in the crushing strength of the iron ore pellets.
In the method for producing iron ore pellets, due to calcining the dolomite at a temperature greater than or equal to the predetermined value in the preparing step S1, the dolomite is present in a miniaturized state in a pellet structure prior to firing, and an effect of increasing the bonding strength of the pellet structure of the iron ore pellets is produced. The crushing strength of the iron ore pellets to be produced can thus be increased. In addition, in the iron ore pellets produced by the method for producing iron ore pellets, a CaO/SiO2 mass ratio is greater than or equal to 0.8 and a MgO/SiO2 mass ratio is greater than or equal to 0.4, resulting in high reducibility.
It is to be noted that the present invention is not limited to the above-described embodiments.
In the first embodiment, only the method of pulverizing the dolomite in the preparing step such that the Blaine specific surface area is greater than or equal to the predetermined value has been described, and in the second embodiment, only the method of calcining the dolomite at a temperature of greater than or equal to the predetermined value in the preparing step has been described; however, these methods may be employed in combination.
In the first embodiment, the method of pulverizing the dolomite in the preparing step has been described; however, dolomite having the Blaine specific surface area greater than or equal to the predetermined value may be prepared in advance. Similarly, in the second embodiment, calcined dolomite may be prepared. In this case, the preparing step may be omitted.
In addition, it is considered that, due to the dolomite being present in a miniaturized state in a structure of the green pellets prior to the firing, the crushing strength of the iron ore pellets to be produced can be increased as described above. Therefore, the treatment in the preparing step is not limited to those of the aforementioned embodiments, and the dolomite may be subjected to another treatment to be present in a miniaturized state in the pellet structure prior to the firing.
In the aforementioned embodiments, the method of producing iron ore pellets by using the production apparatus with the grate kiln system has been described; however, the iron ore pellets may also be produced by using a production apparatus with a straight grate system. In the production apparatus with the straight grate system, the grate furnace includes a traveling grate, a drying chamber, a dehydrating chamber, a preheating chamber, and a firing chamber, and the firing step is completed only in the grate furnace. Specifically, the green pellets are dried, dehydrated, and preheated by a heating gas in the drying chamber, the dehydrating chamber, and the preheating chamber, and finally fired in the firing chamber.
Hereinafter, the present invention is explained in further detail by way of Examples, but the present invention is not in any way limited to these Examples.
Iron ore pellets in which a CaO/SiO2 mass ratio was 1.4 and a MgO/SiO2 mass ratio was 0.8 were produced by the procedure illustrated in
The crushing strength of each of the iron ore pellets thus produced was measured. The results are shown in
The graph in
Note that although the CaO/SiO2 mass ratio was 1.4 and the MgO/SiO2 mass ratio was 0.8 in the present experiment in the present experiment, it is inferred that since the CaO/SiO2 mass ratio of 0.8 and the MgO/SiO2 mass ratio of 0.4, for example, increase the crushing strength, the Blaine specific surface area of the dolomite being greater than or equal to 4,000 cm2/g gives the crushing strength of greater than or equal to 270 kg/P even in the case in which the firing temperature is 1,230° C., by reducing the CaO/SiO2 mass ratio and the MgO/SiO2 mass ratio.
Iron ore pellets in which a CaO/SiO2 mass ratio was 1.40 and a MgO/SiO2 mass ratio was 0.83 were produced by the procedure illustrated in
Regarding each of the iron ore pellets thus produced, measurements were performed on: a percentage of particles having a grain size of less than or equal to 20 μm in the dolomite after the hydration reaction in the balling step; and the crushing strength. The results are shown in
The graph in
By employing the method for producing iron ore pellets according to the present invention, iron ore pellets superior in reducibility and having high crushing strength can be produced. Therefore, the iron ore pellets produced by the present method for producing iron ore pellets can be used in a blast furnace operated with a low reduction agent ratio.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2021-062578 | Apr 2021 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2021/018288 | 5/13/2021 | WO |
