WO2022209014A1

WO2022209014A1 - Raw material particles for production of agglomerate, method for producing raw material particles for production of agglomerate, agglomerate, method for producing agglomerate, and method for producing reduced iron

Info

Publication number: WO2022209014A1
Application number: PCT/JP2021/044584
Authority: WO
Inventors: 隆英樋口; 哲也山本; 光輝照井
Original assignee: Ｊｆｅスチール株式会社
Priority date: 2021-03-31
Filing date: 2021-12-03
Publication date: 2022-10-06
Also published as: TW202239973A; JP7424339B2; AU2021437808A1; US20240167110A1; BR112023019688A2; CA3212055A1; CN117043364A; JP2022157632A; EP4317464A1; EP4317464A4

Abstract

Provided are raw material particles for the production of an agglomerate, able to produce an agglomerate having a higher reducing property. The raw material particles 1 (2) of the present invention, for producing an agglomerate used as raw material for the production of reduced iron comprise: central parts 11 (21) and outer peripheral parts 12 (22) covering the circumference of the central parts 11 (21). The raw material particles are characterized in that the central part 11 has a metal iron-containing substance, the center part 21 has a volatile substance, and the outer peripheral parts 12 (22) have an iron oxide.

Description

Raw material particles for producing agglomerate, method for producing raw material particles for producing agglomerate, agglomerate, method for producing agglomerate, and method for producing reduced iron

The present invention relates to raw material particles for producing agglomerates, a method for producing raw material particles for producing agglomerates, agglomerates, a method for producing agglomerates, and a method for producing reduced iron.

In the steel industry, the blast furnace method has been the mainstream of the pig iron manufacturing process for many years. In the blast furnace method, raw materials containing iron oxide such as sintered ore and coke are charged into the blast furnace from the top of the blast furnace, and hot air is blown into the blast furnace from tuyeres at the bottom of the blast furnace. As a result, the blown hot air reacts with coke in the blast furnace to generate high-temperature reducing gas (mainly carbon monoxide (CO) gas), which heats and reduces the raw material. After that, the raw material is melted and dripped into the blast furnace while being further reduced by coke, and finally stored in the hearth as molten pig iron (pig iron). The stored hot metal is taken out from the tap hole and supplied to the next steelmaking process. Thus, in the blast furnace method, carbonaceous material such as coke is used as a reducing agent to indirectly reduce iron oxide contained in the raw material.

By the way, in recent years, the prevention of global warming has been called for, and there is a strong demand for the reduction of emissions of carbon dioxide (CO ₂ ), which is one of the greenhouse gases. As mentioned above, the blast furnace process uses carbonaceous material as a reducing agent, so a large amount of CO ₂ is generated. Therefore, various blast furnace operating methods have been proposed in which the reducing agent ratio (the amount of reducing agent used per ton of hot metal) is reduced (see, for example, Patent Document 1).

On the other hand, as a method for directly reducing iron oxide contained in raw materials, agglomerates such as fired pellets and sintered bodies of iron ore powder, which are raw materials for reduced iron, are charged from the top of a reducing furnace such as a shaft furnace. In addition, there is a method of producing reduced iron by introducing a gas (CO gas, H gas) as a reducing agent from the lower part of the reducing furnace (for example, Patent Document ₂ ), MIDREX (registered trademark) (Non-Patent Document 1 ) are known. _In this method, if only H2 gas is used as the reducing gas, it is theoretically possible to produce reduced iron that does not emit _CO2 .

Japanese Patent Application Laid-Open No. 2020-45508 Japanese Patent Publication No. 2-46644

In the method described in Patent Document 2 or Non-Patent Document 1, in order to suppress the amount of CO ₂ emissions, it is necessary to reduce the amount of reduction reaction by CO gas and increase the amount of reduction reaction by H ₂ gas. Well, for that purpose, the _H2 concentration of the reducing gas used should be increased.

However, while the reduction reaction with CO gas is an exothermic reaction (+6710 kcal/kmol (Fe ₂ O ₃ )), the reduction reaction with H ₂ gas is an endothermic reaction (-22800 kcal/kmol (Fe ₂ O ₃ )). be. Therefore, if the H ₂ concentration of the reducing gas is increased, an endothermic reaction occurs, the temperature in the furnace drops, and the reduction reaction stagnate, resulting in a decrease in reducibility.

In order to solve the problem of reduced reducibility as described above, agglomerates with high reducibility and raw material particles from which such agglomerates can be produced are desired.

The present invention has been made in view of the above problems, and its object is to provide raw material particles for producing agglomerates, which can produce agglomerates having a higher reducibility than conventional ones. to do.

The present invention for solving the above problems is as follows.

[1] Raw material particles for producing an agglomerate as a raw material for producing reduced iron,
A central portion and an outer peripheral portion that surrounds the central portion,
A raw material particle for producing an agglomerate, wherein the central portion contains a metallic iron-containing substance or a volatile substance, and the outer peripheral portion contains iron oxide.

[2] The raw material particles for producing agglomerates according to [1], wherein the iron oxide contains at least water of crystallization exceeding 4% by mass and/or alumina exceeding 1.5% by mass.

[3] The raw material particles for producing an agglomerate according to [1] or [2], wherein the particle size of the central portion is 2 mm or more and 6 mm or less.

[4] The raw material particle for producing an agglomerate according to any one of [1] to [3], wherein the outer peripheral portion has a thickness of 2 mm or more and 5 mm or less.

[5] A method for producing raw material particles according to any one of [1] to [4] above, wherein the raw material containing iron oxide is pulverized to obtain a raw material powder, and then classified to classify the raw material. A pretreatment step for adjusting the particle size of the powder,
Raw material particles for producing agglomerates, characterized in that the raw material powder whose particle size is adjusted and the metallic iron-containing substance or the volatile substance and the binder are mixed and granulated to obtain the raw material particles. Production method.

[6] The method for producing raw material particles for producing agglomerates according to [5], wherein the metallic iron-containing substance or the volatile substance having a particle size of 2 mm or more and 6 mm or less is used in the granulation step.

[7] The method for producing raw material particles for producing agglomerates according to [5] or [6], wherein in the granulation step, the thickness of the outer peripheral portion is adjusted to 2 mm or more and 5 mm or less.

[8] An agglomerate obtained by firing or sintering the raw material particles according to any one of [1] to [4],
The agglomerated raw material particles are
When the core before firing or sintering has the metallic iron-containing material, the core includes a first portion having the metallic iron-containing material and the metallic iron-containing material surrounding the first portion. Having a three-layer structure having a second portion in which the contained metallic iron is oxidized,
An agglomerate characterized in that, when the core before firing or sintering contains the volatile substance, the core has a hollow structure that is a void.

[9] The raw material particles according to any one of [1] to [4] or the raw material particles produced by the production method according to any one of [5] to [7] are A method for producing an agglomerate, characterized in that the agglomerate is obtained by firing or sintering in an oxidizing atmosphere at a temperature of 1350°C or lower.

[10] The agglomerate described in [8] or the agglomerate manufactured by the manufacturing method described in [9] is charged into a reducing furnace, a reducing gas is introduced into the reducing furnace, and the A method for producing reduced iron, comprising reducing iron oxide contained in the agglomerate with a reducing gas to obtain reduced iron.

[11] The method for producing reduced iron according to [10], wherein a gas containing hydrogen as a main component is used as the reducing gas.

According to the present invention, it is possible to provide raw material particles for producing agglomerates, which can produce agglomerates having a higher reducibility than conventional ones.

It is a figure which shows an example of the particle|grains which comprise the conventional agglomerate. BRIEF DESCRIPTION OF THE DRAWINGS It is a figure which shows the raw material particle|grains for agglomerate manufacture by this invention, (a) has a metal iron containing substance in the center part, (b) has a volatile substance in the center part. BRIEF DESCRIPTION OF THE DRAWINGS It is a figure which shows the particle|grains which comprise the agglomerate by this invention, (a) has a three-layer structure, (b) has a hollow structure.

(Raw material particles for agglomerate production)
Hereinafter, embodiments of the present invention will be described with reference to the drawings. The raw material particles for producing agglomerates according to the present invention are raw material particles for producing agglomerates that serve as raw materials for producing reduced iron, and include a central portion and an outer peripheral portion that surrounds the central portion. The central portion comprises metallic iron-containing substances or volatile substances, and the outer peripheral portion comprises iron oxide.

The present inventors diligently studied raw material particles for producing agglomerates, which can produce agglomerates that are raw materials for producing reduced iron and have higher reducibility than conventional ones. FIG. 1 shows an example of particles that constitute a conventional agglomerate. The particle 100 shown in FIG. 1 comprises a central portion 110 and an outer peripheral portion 120 surrounding the central portion 110 . In the particle 100, the central portion 110 is composed of coarse-grained iron oxide, and the peripheral portion 120 is composed of iron ore fine powder (that is, iron oxide).

The inventors diligently studied ways to increase the reducibility of agglomerates. As a result, the present inventors have come up with the idea of forming the central portion of the particles that constitute the agglomerate from a material that does not require or does not require reduction.

That is, the particles 100 are entirely composed of iron oxide, but in order to reduce the iron oxide in the central portion 110, the reducing gas passes through the outer peripheral portion 120 to reach the central portion 110, and reacts. must be exhausted from the surface of the particle 100. Therefore, reducing the iron oxide in the central portion 110 of the particle 100 requires a longer time than reducing the iron oxide in the outer peripheral portion 120 . This leads to a decrease in reducibility of the particles as a whole.

Therefore, the present inventors have determined that the central portion 110 of the conventional particle 100, which requires a long time for reduction, is replaced by a substance containing metallic iron with a high content of metallic iron or a substance that does not require reduction such as voids. It was thought that the time required for reduction of the particles as a whole could be reduced and the reducibility could be enhanced by configuring with

The inventors of the present invention have found that the agglomerate as described above is a raw material particle in which the core is composed of the metallic iron-containing material or a volatile substance whose large proportion disappears at high temperatures, and the outer periphery is composed of iron ore powder. By manufacturing using, the particles constituting the agglomerate obtained after the agglomeration step (firing step or sintering step) can be in a state where the central part does not need or is not much required to be reduced, as described above. and completed the present invention. Each configuration of the present invention will be described below.

The raw material particles for producing agglomerates of the present embodiment are raw material particles for producing agglomerates that serve as raw materials for producing reduced iron using a reducing gas, and are generally called green pellets. FIG. 2 shows raw material particles for producing agglomerates according to the invention. The raw material particle 1 shown in FIG. 2(a) comprises a central portion 11 having a metallic iron-containing substance and an outer peripheral portion 12 having iron oxide. The raw material particle 2 shown in FIG. 2(b) has a central portion 21 containing volatile substances and an outer peripheral portion 22 containing iron oxide.

<Central area>
The central portion 11 (21) is a portion that constitutes the nucleus of the raw material particle 1 (2), and in the present invention is composed of a substance that does not require reduction with a reducing gas or a substance that does not require much reduction. Specifically, the central portion 11 (21) is composed of a metallic iron-containing substance (volatile substance).

－Substances containing metallic iron－
In the present invention, the metallic iron-containing substance is a substance having a high metallic iron content, specifically a substance having a metallic iron concentration of 70% by mass or more. Examples of such metallic iron-containing substances include reduced iron products produced during the production of reduced iron, sieved products of reduced pellets (pellet chips), and various scraps such as cast iron. Substances can be used. As the metallic iron-containing substance, it is preferable to use a substance having a metallic iron concentration of 90% by mass or more.

- Volatile substances -
On the other hand, the volatile substance is a substance that volatilizes in the agglomeration process (firing process or sintering process), specifically, a substance that has a mass reduction rate of 90% or more at 1000°C. Used paper, organic substances, and the like can be used as such volatile substances. Specifically, polypropylene, woody biomass-based pellets, waste paper, pellets manufactured from paper pulp waste, and the like can be used.

The following describes a suitable raw material particle configuration when the particle size of the entire agglomerate, which is the raw material for producing reduced iron, is 6 to 16 mm, which is used as green pellets. It is preferable that the grain size of the central portion 11 is 2 mm or more and 6 mm or less. If the particle size of the central portion 11 is 2 mm or more, even when the raw material particles 1 are fired or sintered in the agglomeration step, the central portion 11 is not entirely oxidized, leaving the metallic iron-containing substance. The reducibility of the agglomerate can be enhanced. In addition, if the particle diameter of the central portion 11 is 6 mm or less, and the particle diameter of the raw material particles 1 (2) is 6 to 16 mm, the thickness of the coating layer is sufficiently secured, and more new raw materials for reduced iron are used. can be compounded.

<Periphery>
The outer peripheral portion 12 (22) constitutes a coating layer that covers the periphery of the central portion 11 (21), which is the nucleus, of the raw material particle 1 (2). In the present invention, the outer peripheral portion 12 (22) can be made of iron oxide.

The iron source of the outer peripheral portion 12 (22) is preferably composed of iron oxide powder, which is powdery iron oxide. As a result, when reducing the agglomerate, the reducing gas can be circulated through the gaps between the iron oxide powders to efficiently reduce the iron oxide. Also, the outer peripheral portion 12 (22) may contain an auxiliary material such as CaO or MgO.

When the outer peripheral portion 12 (22) is made of iron oxide powder, the particle size is preferably 125 μm or less. If the particle size of the iron oxide powder is 125 μm or less, dense raw material particles 1 (2) with reduced porosity between powders that collapse during transportation without reducing the strength of the raw material particles 1 (2) can be obtained. Granulation can be produced. More preferably, the particle size of the iron oxide powder is 63 μm or less, and even more preferably 45 μm or less.

The thickness of the outer peripheral portion 12 is preferably 2 mm or more and 5 mm or less. If the thickness of the outer peripheral portion 12 is 2 mm or more, it is possible to prevent the layers forming the outer peripheral portion 12 from breaking or collapsing during the firing process. Further, if the thickness of the outer peripheral portion 12 is 5 mm or less, the particle size of the raw material particles 1 (2) can be controlled within the range of 6 mm to 16 mm, and the reaction time in the reduction furnace can be secured.

Also, the iron oxide in the outer peripheral portion 12 (22) can be composed of a relatively low-quality raw material. Specifically, the iron oxide can contain at least more than 4% by weight of water of crystallization and/or more than 1.5% by weight of alumina. Conventionally, in the process of producing reduced iron using a reducing furnace, a high-quality raw material with a high content of iron oxide has been used. However, in recent years, the quality of iron ore powder for producing agglomerates that serve as raw materials for reduced iron has been declining due to depletion of high-quality iron ore. Low-grade iron ore contains a large amount of water of crystallization and gangue (alumina (Al ₂ O ₃ ) and silica (SiO ₂ )). Also, the gangue melts during the firing process, reducing the strength of the agglomerate.

In order to compensate for such a decrease in strength, it is effective to reduce the water of crystallization contained in the iron ore in the drying process and to increase the amount of heat for firing. Therefore, there arises a problem that the reducibility of the agglomerate is lowered. When the reducibility of the agglomerate is lowered, it takes more time to reduce the agglomerate in the reduced iron production process, resulting in a reduced production efficiency of reduced iron. Thus, there is a trade-off relationship between the strength and reducibility of the agglomerate.

As a method of achieving both strength and reducibility of the agglomerate, for example, it is conceivable to make the size of the raw material particles smaller than before. However, in this case, in the granulation process, it is necessary to precisely control the granule size when granulating the raw material particles before firing or sintering, which is difficult in the operation using a conventional granulator. be. Further, when charged into a reducing furnace, fine pellets may impede air permeability, which is not preferable in terms of operation.

In this regard, the raw material particles 1 (2) according to the present invention have the central portion 11 (21) composed of metallic iron-containing substances (volatile substances), and are composed of substances that do not require or require little reduction. Therefore, even when low-grade iron ore, specifically iron oxide constituting the outer peripheral portion, contains at least more than 4% by mass of water of crystallization and/or more than 1.5% by mass of alumina, a dense mass It is possible to compensate for the decrease in reducibility due to the production of the product. Thus, the raw material particles 1 (2) according to the present invention can be used to produce an agglomerate having both strength and reducibility. As the iron oxide, for example, iron ore produced in Australia or iron ore produced in India, which contain relatively many impurities, can be used.

The particle size of the raw material particles 1 (2) is preferably 6 mm or more and 16 mm or less. If the particle size of the raw material particles 1 (2) is 6 mm or more, air permeability in the furnace is secured when iron oxide contained in the agglomerate obtained by agglomerating the raw material particles 1 (2) is reduced. can operate while Further, if the particle size of the raw material particles 1(2) is 16 mm or less, the delay of reduction inside the raw material particles 1(2) can be minimized, and an agglomerate with a high reduction rate can be produced. Preferably, the particle size of the raw material particles 1 (2) is 9 mm or more and 16 mm or less.

Further, the ratio of the central portion 11 to the entire raw material particles 1 is preferably 5% by mass or more and 50% by mass or less. If the ratio of the central portion 11 is 5% by mass or more, an agglomerate with high reducibility can be obtained. Moreover, if the ratio of the central portion 11 is 50% by mass or less, a larger amount of new raw material for reduced iron can be blended while ensuring the thickness of the outer peripheral portion 12 that is the coating layer. More preferably, the proportion of central portion 11 is 10% by mass or more and 20% by mass or less.

(Method for producing raw material particles for producing agglomerates)
The method for producing raw material particles for producing agglomerates according to the present invention is a method for producing the raw material particles according to the above-described present invention, wherein the raw material containing iron oxide is pulverized to make raw material powder, and then classified and classified as described above. A pretreatment step for adjusting the particle size of the raw material powder, and mixing and granulating the raw material powder with the adjusted particle size, a metallic iron-containing substance or a volatile substance, and a binder to obtain raw material particles according to the present invention. and

As described above, the raw material particles for producing agglomerates according to the present invention have agglomerate having a higher reducibility than conventional ones by forming the central portion of a substance that does not require reduction or a substance that does not require much reduction. It is characterized by being manufacturable. The raw material particles according to the present invention can be produced using a known method for producing green pellets. Each step will be described below.

First, in the pretreatment process, the pretreatment necessary for the granulation process, which is the post-process, is performed. Specifically, a raw material having iron oxide containing 4% by mass or less of water of crystallization and/or 1.5% by mass or less of alumina, such as high-quality iron ore, or 4% by mass, such as low-quality iron ore % of crystal water or more than 1.5% by mass of alumina is pulverized, and the obtained raw material powder is classified to adjust its particle size. The raw material of iron ore can be pulverized using a ball mill or the like. In addition, classification can be performed using a rotating rotor, a sieve, or the like.

Next, in the granulation process, the raw material powder whose particle size has been adjusted in the pretreatment process, metallic iron-containing substances or volatile substances, and binders such as quicklime and bentonite are mixed and granulated. These are also component adjustment materials for CaO and MgO. This can be done using a pelletizer such as a disc pelletizer, a drum mixer or the like. In this way, raw material particles for agglomerate production can be produced.

As described above, in the granulation step, it is preferable to use a metallic iron-containing substance or a volatile substance having a particle size of 2 mm or more and 6 mm or less. Also, as described above, it is preferable to adjust the thickness of the outer peripheral portion to 2 mm or more and 5 mm or less in the granulation step.

(Agglomerate)
The agglomerate according to the present invention is an agglomerate obtained by firing or sintering the raw material particles for producing the agglomerate according to the present invention, and the agglomerated raw material particles are fired Alternatively, when the core before sintering has a metallic iron-containing substance, the core has a first portion having a metallic iron-containing substance, and the metallic iron contained in the metallic iron-containing substance covering the first portion is oxidized. It is characterized by having a three-layered structure having a second portion formed thereon, and having a hollow structure in which the central portion is a void when the central portion contains a volatile substance before firing or sintering.

As described above, the raw material particles for producing agglomerates according to the present invention are configured so that the central part thereof contains metallic iron-containing substances or volatile substances. When the central part 11 of the raw material particle 1 has a metallic iron-containing substance, when the raw material particle 1 is fired or sintered, the outer peripheral part 12 of the central part 11 is formed by heat during the firing process or the sintering process. The metallic iron in the adjacent portion is oxidized, leaving the metallic iron-containing material unoxidized inside. As a result, as shown in FIG. 3(a), the particles 3 constituting the agglomerate consisted of a first portion 31a having a metallic iron-containing substance and an oxidized metallic iron covering the first portion 31a. The outer peripheral portion 32 has a three-layer structure including the second portion 31b and iron oxide.

On the other hand, when the central portion 21 of the raw material particle 2 contains a volatile substance, when the raw material particle 2 is fired or sintered, the volatile substance in the central portion 21 volatilizes due to heat during the firing process or the sintering process. As a result, as shown in FIG. 3B, the particles 4 constituting the agglomerate have a hollow structure in which the central portion 41 is void and the outer peripheral portion 42 contains iron oxide.

Since the

particles

3 and 4 shown in FIGS. 3(a) and 3(b) have

central portions

31a and 41 that do not require reduction, the agglomerate according to the present invention composed of

such particles

3 and 4 is , it has a higher reducibility than the conventional one.

In addition, the particle 3 has a stronger structure because the layer (second portion) 31b formed by oxidation of the metallic iron-containing material forming the central portion 11 of the raw material particle 1 forms a shell. Regarding the particles 4, although a shell like the layer (second portion) 31b of the particles 3 is not formed, the hollow portion A dense sintered layer is formed on the inner wall texture of 41 . As a result, the particle 4 has a higher strength than a structure that is hollow from the beginning, due to the effect of positively applying the amount of heat from the inside.

(Method for producing agglomerate)
In the method for producing an agglomerate according to the present invention, the raw material particles according to the present invention described above or the raw material particles produced by the method for producing raw material particles according to the present invention are fired or fired in an oxidizing atmosphere at 1200 ° C. or higher and 1350 ° C. or lower. It is characterized by forming an agglomeration by binding to obtain an agglomerate.

The raw material particles for producing agglomerates according to the present invention or the raw material particles produced by the method for producing raw material particles according to the present invention have a core containing a metallic iron-containing substance or a volatile substance, and an outer peripheral portion containing an oxidized substance. have iron; By firing or sintering such raw material iron powder in an oxidizing atmosphere at 1200 ° C. or more and 1350 ° C. or less to agglomerate it, when the center part of the raw material particle has a metallic iron-containing substance, it is adjacent to the outer peripheral part Some of the metallic iron is oxidized, while the core of the raw material particles volatilizes if it has volatiles. As a result, the particles constituting the agglomerates have a three-layer structure as shown in FIG. 3(a) or a hollow structure as shown in FIG. An agglomerate having properties can be obtained.

The firing of the raw material particles can be performed using a rotary kiln or the like. Specifically, the raw material particles for agglomerate production according to the present invention described above or the raw material particles produced by the method for producing raw material particles according to the present invention are charged into a rotary kiln and placed in the air at 1200 ° C. or higher and 1350 ° C. or lower. placed in an oxidizing atmosphere such as Thereby, fired pellets can be obtained.

In addition, sintering of raw material particles can be performed using a sintering machine. Specifically, the raw material particles for agglomerate production according to the present invention described above or the raw material particles produced by the method for producing raw material particles according to the present invention are mixed with granulated particles obtained by granulating conventional raw material particles. and placed in an oxidizing atmosphere at 1200° C. or higher and 1350° C. or lower. Thereby, a sintered ore can be obtained.

(Method for producing reduced iron)
In the method for producing reduced iron according to the present invention, the agglomerate according to the present invention described above or the agglomerate produced by the method for producing an agglomerate according to the present invention is charged into a reducing furnace, and a reducing gas is introduced into the reducing furnace. and reducing iron oxide contained in the agglomerate to obtain reduced iron.

As described above, the agglomerate according to the present invention or the agglomerate produced by the method for producing an agglomerate according to the present invention has higher reducibility than conventional ones. By charging such an agglomerate into a reducing furnace such as a shaft furnace and introducing a reducing gas, reduced iron can be produced efficiently.

In the present invention, the reducing gas includes coke oven gas, gas obtained by reforming natural gas ₍ including hydrocarbon as a component), mixed gas of CO gas and H2 gas, H2 gas ₍ _H2 concentration is 100 % gas) can be used, but it is preferable to use a gas containing H ₂ as a main component as the reducing gas. Here, "a gas containing H ₂ as a main component" means a gas having an H ₂ concentration of 50% by volume or more. This makes it possible to reduce CO ₂ emissions.

The H ₂ concentration of the reducing gas is preferably 65% by volume or more. Thereby, the CO ₂ emission reduction effect can be further enhanced. _The H2 concentration of the reducing gas is more preferably 70% by volume or more, more preferably 80% by volume or more, even more preferably 90% by volume or more, and most preferably 100% by _volume , that is, using H2 gas as the reducing gas. . By using H2 gas as the reducing gas, reduced iron can be produced without _emitting _CO2 .

Examples of the present invention will be described below, but the present invention is not limited to the examples.

(Conventional example 1)
Using Brazilian iron ore whose chemical composition is shown in Table 1, fired pellets were produced. Specifically, first, the iron ore was pulverized and the obtained iron ore powder was classified to obtain iron ore powder having a particle size of −63 μm. Next, the iron ore powder and quicklime as a binder were mixed, and green pellets having a diameter of 12 mm were produced while adjusting the humidity using a pelletizer. Then, the produced green pellets were fired in the atmosphere at 1350° C. for 60 minutes. In this way, fired pellets were produced as an agglomerate according to Conventional Example 1. When the reducibility value of the obtained fired pellets was determined according to JIS-M8713, it was 60%.

(Conventional example 2)
A sintered ore was prepared by using a raw material powder obtained by mixing Brazilian iron ore and Australian iron ore whose composition is shown in Table 1 at a ratio of 50:50. Specifically, first, the solid iron ore was granulated together with auxiliary raw materials limestone, return ore and coke fine to produce granulated particles. The average diameter of the produced granulated particles was about 3 to 4 mm, and core particles (concentration of iron: 57% by mass) of about 1 mm at maximum were contained inside the particles. The granulated particles thus obtained were charged into a small sintering tester and sintered. For sintering, an iron container with a packed bed height of 600 mm and a diameter of 300 mm was used, and sintering was performed under a constant differential pressure with a suction negative pressure of 6.9 kPa. The obtained sintered ore was dropped four times from a height of 2 m, and sintered ore particles having a particle size of 19 to 22 mm were selected from the obtained sintered ore. Thus, a sintered ore as an agglomerate according to Conventional Example 2 was produced. When the reducibility value of the obtained sintered ore was determined according to JIS-M8713, it was 65 to 70%.

(Invention Example 1)
In the same manner as in Conventional Example 1, fired pellets were produced as agglomerates according to Invention Example 1. However, when producing green pellets (raw material particles) for producing agglomerates, DRI powder obtained in the reduced iron production process (iron concentration: 80.4% by mass, particle size: 3 to 5 mm (5 mm Under the sieve, 3 mm above the sieve) and metallization ratio (=reduced iron ratio/total iron content): 80%) were added to prepare green pellets (raw material particles) having the above DRI powder as the center. All other conditions are the same as in Conventional Example 1. The reducibility value of the fired pellets thus obtained was found to be 80%.

(Invention Example 2)
In the same manner as in Conventional Example 1, fired pellets were produced as an agglomerate according to Invention Example 2. However, when producing green pellets (raw material particles) for agglomerate production, DRI powder obtained in the reduced iron production process (iron concentration: 75.2% by mass, particle size: 3 to 5 mm (5 mm Under the sieve and above the sieve of 3 mm), metallization ratio (=reduced iron ratio/total iron content): 65%) was added to prepare green pellets (raw material particles) having the above DRI powder as the center. All other conditions are the same as in Conventional Example 1. The value of the reducibility of the obtained fired pellets was determined to be 78%.

(Invention example 3)
In the same manner as in Conventional Example 2, a sintered ore as an agglomerate according to Invention Example 3 was produced. However, the granulated particles are produced using only Australian iron ore, and the obtained granulated particles are mixed with green pellets produced in the same manner as in Invention Example 1 to produce a mixed granulated raw material. Then, the obtained mixed granulated raw material was put into a small sintering tester and sintered. All other conditions are the same as in Conventional Example 2. The reducibility value of the obtained sintered ore was determined to be 90%.

(Invention Example 4)
A sintered ore as an agglomerate according to Invention Example 4 was produced in the same manner as in Invention Example 3. However, the green pellets prepared by the same method as in Invention Example 2 were used. All other conditions are the same as in Invention Example 3. It was 84% when the value of the reducibility of the obtained sintered ore was calculated|required.

(Invention example 5)
A sintered ore as an agglomerate according to Invention Example 4 was produced in the same manner as in Invention Example 1. However, polypropylene particles (diameter: 3-5 mm) were added in place of the DRI powder when producing the green pellets. All other conditions are the same as in Invention Example 1. The value of the reducibility of the obtained fired pellets was determined to be 79%.

<Evaluation of reducibility of agglomerates>
As described above, in Conventional Examples 1 and 2, the reducibility of the sintered ore was about 60-70%, whereas the reducibility of the sintered ore of Invention Examples 1 to 5 was 79%. As described above, the reducibility was higher than that of Conventional Examples 1 and 2. In addition, from the comparison between Invention Examples 1 and 2, and between Invention Examples 3 and 4, the higher the metallization rate of the central portion of the green pellet (raw material particle), the higher the reducibility value. I know it will be.

<Evaluation of strength of agglomerate>
The agglomerates according to Invention Examples 1 to 5 had strength comparable to that of the agglomerates according to Conventional Examples 1 and 2, and could be used for producing reduced iron without any problem. Thus, the agglomerates according to Invention Examples 1 to 5 have both strength and reducibility.

According to the present invention, it is possible to provide raw material particles for producing agglomerates, which can produce agglomerates having a higher reducibility than conventional ones, and is therefore useful in the steel industry.

1, 2

raw material particles

3, 4

particles

11, 21, 31, 41 constituting the sintered ore

central portion

12, 22, 32, 42 outer peripheral portion 31a first portion 31b second portion

Claims

Raw material particles for producing an agglomerate as a raw material for producing reduced iron,
A central portion and an outer peripheral portion that surrounds the central portion,
A raw material particle for producing an agglomerate, wherein the central portion contains a metallic iron-containing substance or a volatile substance, and the outer peripheral portion contains iron oxide.
The raw material particles for producing agglomerates according to claim 1, wherein the iron oxide contains at least more than 4% by mass of water of crystallization and/or more than 1.5% by mass of alumina.
The raw material particles for producing agglomerates according to claim 1 or 2, wherein the particle size of the central part is 2 mm or more and 6 mm or less.
The raw material particles for producing agglomerates according to any one of claims 1 to 3, wherein the outer peripheral portion has a thickness of 2 mm or more and 5 mm or less.
A method for producing raw material particles according to any one of claims 1 to 4,
A pretreatment step of pulverizing the raw material containing iron oxide to obtain a raw material powder, and then classifying the raw material powder to adjust the particle size of the raw material powder;
Raw material particles for producing agglomerates, characterized in that the raw material powder whose particle size is adjusted and the metallic iron-containing substance or the volatile substance and the binder are mixed and granulated to obtain the raw material particles. Production method.
The method for producing raw material particles for producing agglomerates according to claim 5, wherein the metallic iron-containing substance or the volatile substance having a particle size of 2 mm or more and 6 mm or less is used in the granulation step.
The method for producing raw material particles for producing agglomerates according to claim 5 or 6, wherein in the granulation step, the thickness of the outer peripheral portion is adjusted to 2 mm or more and 5 mm or less.
An agglomerate obtained by firing or sintering the raw material particles according to any one of claims 1 to 4,
The agglomerated raw material particles are
When the core before firing or sintering has the metallic iron-containing material, the core includes a first portion having the metallic iron-containing material and the metallic iron-containing material surrounding the first portion. Having a three-layer structure having a second portion in which the contained metallic iron is oxidized,
An agglomerate characterized by having a hollow structure in which the central portion is a void when the central portion contains the volatile substance before firing or sintering.
The raw material particles according to any one of claims 1 to 4, or the raw material particles produced by the method for producing raw material particles for producing agglomerates according to any one of claims 5 to 7, are A method for producing an agglomerate, characterized in that the agglomerate is obtained by firing or sintering in an oxidizing atmosphere at a temperature of 1350°C or lower.
The agglomerate according to claim 8 or the agglomerate produced by the method for producing an agglomerate according to claim 9 is charged into a reducing furnace, a reducing gas is introduced into the reducing furnace, and the reducing A method for producing reduced iron, comprising reducing iron oxide contained in the agglomerate with a gas to obtain reduced iron.
The method for producing reduced iron according to claim 10, wherein a gas containing hydrogen as a main component is used as the reducing gas.