WO2015045670A1

WO2015045670A1 - Method for manufacturing granular iron

Info

Publication number: WO2015045670A1
Application number: PCT/JP2014/071534
Authority: WO
Inventors: 修三伊東; 泰二畠山; 昌麟王; 杉立　宏志
Original assignee: 株式会社神戸製鋼所
Priority date: 2013-09-25
Filing date: 2014-08-18
Publication date: 2015-04-02
Also published as: US20160237514A1; CN105555973A; JP2015063740A; ZA201601918B

Abstract

Provided is a method for manufacturing granular iron, the method being capable of improving the quality of the granular iron by preventing re-oxidation of reduced iron obtained by heating and reducing agglomerates or of granular iron obtained by melting and condensing said reduced iron in a moving bed-type heating furnace. A method for manufacturing granular iron by charging and heating agglomerates containing iron oxide and a carbonaceous reducing agent on the furnace bottom of a moving bed-type heating furnace and, after reducing and melting the iron oxide in said agglomerates, discharging to the outside of the furnace the granular iron obtained and collecting same. The agglomerates have a covering layer containing a fluid carbon material on the surface.

Description

Production method of granular iron

The present invention, for example, heats an agglomerate containing iron oxide such as iron ore and a carbon-containing reducing agent (hereinafter sometimes referred to as “carbonaceous reducing agent”), and oxidizes the agglomerate. The present invention relates to a method for producing granular iron by reducing and melting iron.

As a method for producing granular iron by heating an agglomerate containing iron oxide and a carbonaceous reducing agent, for example, the technique of Patent Document 1 is known. In this document, as a method for producing a solid metal product from carbon containing a metal bearing compound, the surface of a molded body containing carbon and the metal bearing compound is coated with a treatment substance, and this is supplied onto a hearth and heated. In addition, it is described that the coating layer contains a carbonaceous material.

U.S. Patent No. 6214087

By the way, the agglomerate charged on the hearth of the moving bed type heating furnace is heated by gas heat transfer or radiant heat by a heating burner provided in the furnace, and the iron oxide contained in the agglomerate is converted into a carbonaceous reducing agent. To produce granular iron. However, when a heating burner is used as a heating means, an atmospheric gas stream is generated in the furnace. Since this atmospheric gas contains an oxidizing gas such as carbon dioxide and water vapor, the reduced iron obtained by heating and reducing the agglomerates, and the granular iron obtained by melting and agglomerating the reduced iron, Reoxidation may occur with this oxidizing gas. When the reduced iron or granular iron is reoxidized, the amount of FeO in the slag produced as a by-product during the production of reduced iron increases, so the ratio of the amount of sulfur in the slag (S) to the amount of sulfur in the granular iron [S] (hereinafter, This may be referred to as a sulfur distribution ratio and may be expressed as (S) / [S].) When the amount of sulfur in granular iron increases, the quality of granular iron deteriorates. In addition, FeO in the slag reacts with the generated semi-molten iron and carbon [C] contained in the molten iron and decarburizes this, so the amount of carbon in the granular iron is reduced. In addition, due to the decarburization reaction, many fine CO gas bubbles are present in the slag, and as a result of large expansion, intense slag forming occurs, covering the semi-molten and molten granular iron that is in the process of agglomeration. Therefore, the heat supplied from the upper side of the heating furnace is shut off, the reaction time is significantly increased, and the productivity is lowered. In addition, when slag forming occurs, the shape of the granular iron becomes irregular, or separation between the granular iron and a part of the slag becomes inadequate, resulting in a problem of reducing the quality of the granular iron.

The present invention has been made paying attention to the above-mentioned circumstances, and the object thereof is obtained by reducing and agglomerating the agglomerate by heating, and by melting and agglomerating the reduced iron. An object of the present invention is to provide a method for producing granular iron that can prevent the granular iron from being reoxidized in a moving bed heating furnace and improve the quality of the granular iron.

The method for producing granular iron according to the present invention that has solved the above-mentioned problem is to charge an agglomerate containing iron oxide and a carbonaceous reducing agent on the hearth of a moving bed heating furnace, A method for producing granular iron in which iron oxide in an agglomerate is reduced and melted, and the obtained granular iron is discharged outside the furnace and recovered. The agglomerate has fluidity on the surface. It has a gist in that it has a coating layer containing a carbonaceous material.

The carbonaceous material may be at least one selected from the group consisting of bituminous coal, subbituminous coal, and lignite. The average thickness of the coating layer is preferably more than 0.30 mm.

The agglomerated material is obtained by agglomerating a mixture containing iron oxide and a carbonaceous reducing agent in a first granulator to form a core part, and then a carbon material having fluidity on the surface of the obtained core part. It can manufacture by forming the coating layer containing this with a 2nd granulator.

It is preferable that the top of the coating layer does not become lower than the top of the granular iron while heating the agglomerate.

It is preferable that the coating layer becomes a shell-like coke while heating the agglomerate. It is preferable that the agglomerate is charged in a single layer on the hearth. Prior to charging the agglomerate onto the hearth, it is preferable to lay a carbonaceous reducing agent on the hearth.

The granular iron preferably has a C content of 2.5% by mass or more. The granular iron preferably has an S content of 0.120% by mass or less.

In producing granular iron by heating, reducing and melting iron oxide contained in the agglomerate, according to the present invention, the carbonaceous material having fluidity on the surface of the core containing iron oxide and carbonaceous reducing agent The agglomerate having a coating layer containing slag is used, so that the coating layer expands and transforms while the agglomerate is heated, so-called coke, petal-like, shell-like coke. Form. This shell-like coke prevents atmospheric gas from oxidizing the core part and acts as a windbreak wall for protecting the core part. As a result, reoxidation of reduced iron obtained by heating and reducing the agglomerates and granular iron obtained by melting and agglomerating the reduced iron is suppressed, and slag in the by-product during the production of granular iron is suppressed. An increase in the amount of FeO can be suppressed. Therefore, the amount of sulfur contained in granular iron can be reduced, and the quality of granular iron can be improved. Furthermore, since the amount of FeO in the slag does not increase, the decarburization of carbon [C] contained in the semi-molten iron and molten iron to be generated can be suppressed, the carbon content of the granular iron can be increased, and intense slag forming Therefore, the generation of irregular shaped iron can be prevented, the separation of granular iron and slag can be improved, and the quality of the granular iron can be improved.

FIG. 1 is a schematic diagram showing a state when an agglomerate charged on the hearth of a heating furnace is heated. FIG. 2 is a schematic diagram showing the step (4) in FIG. 1 in more detail. (1) to (3) in FIG. 3 are photographs, which substitute for a drawing, taken of the agglomerate when the agglomerate was actually heated in a heating furnace. (1) in FIG. 4 is a drawing-substituting photograph in which a cross section of the reduced iron collected in the latter stage of solid reduction is photographed with an optical microscope, and (2) in FIG. 4 is a drawing obtained by performing image processing on (1) in FIG. It is a substitute photo. (1) in FIG. 5 is a drawing-substituting photograph in which a cross section of the reduced iron collected just before melting and aggregation is taken with an optical microscope, and (2) in FIG. 5 is a drawing obtained by performing image processing on (1) in FIG. It is a substitute photo. (1) in FIG. 6 is a drawing-substituting photograph showing a state in which granular iron after melting and aggregation is covered with violently formed slag when an agglomerate having no coating layer belonging to the prior art is heated. FIG. 6 (2) shows a drawing substitute photograph in which the collected granular iron is photographed, and FIG. 6 (3) shows a drawing substitute photograph in which the collected slag is photographed. (1) in FIG. 7 is a drawing-substituting photograph in which the state after melting and agglomeration is completed is obtained for the agglomerate obtained by forming a coating layer containing a carbon material having fluidity on the surface of the core part. (2) in FIG. 7 shows a drawing substitute photograph in which the collected granular iron is photographed, and (3) in FIG. 7 shows a drawing substitute photograph in which the collected slag is photographed. (1) to (4) in FIG. 8 are schematic views showing a cross section of a petal-like, shell-like coke formed while heating the agglomerate when the thickness of the coating layer is changed. It is. (1) in FIG. No. 4 shown in Table 5 is a drawing substitute photograph taken immediately after heat reduction treatment of No. 4 and (2) of FIG. FIG. 9 (3) is a drawing substitute photograph taken immediately after the heat reduction treatment of No. 5 and No. 5 shown in Table 5. 6 is a drawing substitute photograph taken immediately after the heat reduction treatment of 6.

The present inventors have intensively studied in order to prevent reoxidation of granular iron obtained by heating, reducing, and melting iron oxide contained in the agglomerate and to improve the quality of granular iron. In particular, studies have been made to reduce the amount of sulfur contained in granular iron, increase the amount of carbon contained in granular iron, prevent generation of irregular shaped granular iron, and improve separation of granular iron and slag. . As a result, it was found that the above problem can be solved satisfactorily by using an agglomerate having a coating layer containing a carbonaceous material having fluidity on the surface of the core containing iron oxide and a carbonaceous reducing agent. Completed the invention.

First, a mechanism capable of preventing reoxidation of granular iron and improving the quality of granular iron in the method for producing granular iron according to the present invention will be described with reference to the drawings. FIG. 1 is a schematic diagram showing a state when an agglomerate charged on the hearth of a heating furnace is heated. FIG. 2 is a schematic diagram showing the step (4) in FIG. 1 in more detail. (1) in FIG. 3 is a drawing-substituting photograph in which the coating layer is expanded and coked immediately after the agglomerate is charged in the heating furnace. 3) is a drawing of a petal-like, coke-like shell, coke, and granular iron and slag grains in an agglomerate that has been heated, melted and agglomerated with a coating layer on the surface of the core. It is a substitute photo.

In the production method of the present invention, an agglomerate having a coating layer containing a carbon material having fluidity on the surface of a core part containing iron oxide and a carbonaceous reducing agent is placed on the hearth of a moving bed type heating furnace. Charge to heat. A schematic diagram of the agglomerate charged into the heating furnace is shown in FIG. In (1) of FIG. 1, 1 is a nucleus part, 2 is a coating layer, 3 has shown the agglomerate, respectively.

The core part 1 contains iron oxide and a carbonaceous reducing agent, and may further contain a flux or a binder as necessary. The component composition of the core 1 is the same as the conventional one, and will be described in detail later.

The coating layer 2 includes a carbon material having fluidity, and may further include a binder as necessary. The component composition and thickness of the coating layer 2 will be described in detail later.

The inside of the moving bed type heating furnace is usually heated and held at about 1350 ° C. to 1550 ° C. by a heating burner. When the agglomerate 3 is charged on the hearth in the heating furnace, the agglomerate 3 is heated by gas heat transfer and radiant heat by a heating burner. At this time, the coating layer 2 is once fluidized and expanded as a whole as shown in (2) of FIG. 1 to quickly form a solid and shell-like coke. Although cracks are generated at the top of the shell-like coke, they are connected as a whole and form a shell-like spherical body.

FIG. 3 (1) shows a state where the coating layer 2 is expanded by heating and cracks are generated in the coating layer 2 at the top of the agglomerate. As shown in (1) of FIG. 3, many cracks are generated in the coating layer 2, but they are connected as a whole and form a shell-like spherical body. Since the shell-like spherical body is composed of solid coke, it is excellent in heat transfer. Therefore, when the shell-like spherical body is heated by the radiant heat in the heating furnace, the core part 1 is also heated by the heat transfer.

When the heating is further continued, as shown in (3) of FIG. 1, in the core 1, the reduction of iron oxide proceeds by the action of the carbonaceous reducing agent, and solid reduced iron is formed. At this time, the reduction of the iron oxide constituting the core part 1 proceeds from the top side of the core part 1, and reduced iron 4 is generated.

When the heating is further continued, as shown in FIG. 1 (4), the iron oxide constituting the core 1 is sufficiently reduced, and the granular iron 6 made of reduced iron and the granular iron 6 are generated. It is separated into slag 7 that is sometimes by-produced. The state at this time is shown in FIG.

On the other hand, as shown in FIG. 1 (3) and FIG. 1 (4), the coating layer 2 covering the core 1 is formed with a shell-like spherical body around the core 1, The covering layer 2 is gradually oxidized and consumed by the oxidizing gas contained in the atmospheric gas and becomes thinner. At this time, the top portion of the coating layer 2 is oxidized and consumed earlier than the bottom portion, and gradually disappears. Therefore, when the coating layer thickness is thin, as shown in (3) of FIG. 1 and (4) of FIG. An opening is formed at the top. FIG. 3B shows a drawing substitute photograph of the situation at this time. As shown in (2) of FIG. 3, it turns out that the shell-shaped coke formed from the coating layer 2 in which the opening was formed in the top part has a petal shape. In addition, since the shell-shaped coke formed becomes thick when the coating layer is thick, the reaction is completed in a state in which the core is wrapped without opening the upper portion of the shell-shaped coke. Therefore, it is clear that it works more effectively to prevent reoxidation by the atmospheric gas. Both the case where the upper part of the shell-like coke is opened and the case where it is not opened fall within the scope of the present invention.

As shown in FIG. 1 (4), the shell-like coke formed from the coating layer 2 having an opening at the top is formed so as to wrap around the granular iron 6. Therefore, in the shell-like coke, reduced iron obtained by heating and reducing the core part, and granular iron obtained by melting and agglomerating the reduced iron are reoxidized by the atmospheric gas in the heating furnace. It has the effect | action which prevents this. This will be described in more detail with reference to FIG.

The arrows shown in FIG. 2 indicate the flow of the atmospheric gas. According to the production method of the present invention, the solid reduction of the iron oxide contained in the core part 1 is completed, and while the melting and aggregation proceed, the reduction obtained by heating and reducing the core part as shown in FIG. A shell-like coke is formed from the coating layer 2 so as to enclose the iron and the granular iron 6 and the slag 7 obtained by melting and agglomerating the reduced iron. Therefore, the atmospheric gas in the heating furnace is reduced iron obtained by heat reduction of an agglomerate having a coating layer on the surface of the core, or granular obtained by melting and agglomerating the reduced iron It becomes difficult to contact the iron 6 directly. The atmospheric gas contains carbon dioxide gas (CO ₂ gas) and moisture (H ₂ O). When the carbon dioxide gas comes into contact with the shell-like coke formed from the coating layer 2, The carbon dioxide gas is reduced by the shell-like coke to generate carbon monoxide gas (CO gas) as shown in the following formula (1). Further, when the moisture contained in the atmospheric gas comes into contact with the shell-like coke formed from the coating layer 2, the moisture is reduced by the shell-like coke, and as shown in the following formula (2), Gas (H ₂ ) and carbon monoxide gas (CO gas) are generated. As a result, the reduction degree RD of the atmospheric gas around the shell-shaped coke formed from the coating layer 2 is increased, and the agglomerate having the coating layer on the surface of the core is reduced by heating. Reoxidation of the obtained reduced iron and granular iron obtained by melting and agglomerating the reduced iron is prevented. Note that the reduction degree RD of the atmospheric gas is obtained by the following formula (3).
CO ₂ + C = 2CO (1)
H ₂ O + C = H ₂ + CO (2)
RD = [(CO + H ₂ ) / (CO + H ₂ + CO ₂ + H ₂ O)] × 100 (3)

According to the production method of the present invention, while heating the agglomerate having the coating layer 2 on the surface of the core part, reduced iron obtained by heating and reducing the agglomerate, The granular iron obtained by melting and agglomerating the reduced iron is sufficiently protected from the oxidizing gas by the shell-like coke formed from the coating layer 2, and the reduced iron and the granular iron are recycled. Oxidation can be prevented. The shell-like coke formed from the coating layer 2 has a petal shape while the agglomerate is heated, and the shell-like coke formed from the coating layer 2 The height is not constant, and the effect of the present invention can be obtained even if a part of the height is missing.

On the other hand, when only the core part 1 in which the coating layer containing the fluid carbonaceous material is not formed as in the prior art is heated in the heating furnace, the reduction of the whole core part 1 proceeds in the solid reduction phase. However, since the core part 1 itself is directly exposed to the atmospheric gas, the reduced iron obtained by heating and reducing the core part 1 with the oxidizing gas contained in the atmospheric gas, or the reduced iron melts and aggregates. Part of the granular iron obtained in this way is reoxidized.

FIG. 4 and FIG. 5 show a photograph substituted for a drawing of the reduced iron obtained by heating only the core 1 where the coating layer containing the carbon material having fluidity is not formed. FIG. 4 shows a drawing-substituting photograph in which a cross section of the reduced iron collected in the latter stage of the solid reduction is taken with an optical microscope. FIG. 5 shows a drawing-substituting photograph in which a cross section of the reduced iron collected immediately before melting and aggregation is taken with an optical microscope. 4 and 5, (1) shows a photomicrograph of a cross section taken, and (2) shows a color-coded portion of the reduced portion and the reoxidized portion in the cross section shown in (1). The schematic diagram shown is shown.

As shown in (2) of FIG. 4 and (2) of FIG. 5, it can be seen that part of the metallic iron once generated is reoxidized into FeO in the upper part of the reduced iron.

The FeO produced by re-oxidation quickly melts into the slag that is separated and produced during the melting and agglomeration phase, and increases the FeO concentration in the slag. Further, when FeO melts into slag, it reacts with the generated semi-molten iron and carbon [C] contained in the molten iron and decarburizes this, so that many fine CO gas bubbles are inherent in the slag. As a result of the large expansion, severe slag foaming occurs, and the semi-molten and molten granular iron that is in the process of agglomeration is covered. For this reason, the heat supplied from above the heating furnace is shut off, the reaction time is significantly increased, and the productivity is lowered. Moreover, when slag forming occurs, the shape of the granular iron becomes irregular, or separation between the granular iron and a part of the slag becomes inadequate, resulting in a problem of reducing the quality of the granular iron. The generation of the oxidizing gas is caused by combustion of a combustion burner used for heating in the heating furnace, combustion of combustible gas generated in accordance with a reduction reaction, leakage of air from the outside to the inside of the heating furnace, and the like.

In addition, when using the agglomerate which has the coating layer containing the carbonaceous material which has fluidity | liquidity like the manufacturing method of this invention, the reduced iron obtained by heat-reducing the agglomerate or Since re-oxidation of the granular iron obtained by melting and agglomerating the reduced iron is prevented, the granular iron and slag are separately melted and separated during the melting and agglomeration period. As a result, no slag forming occurs.

As described above, in the production method of the present invention, an agglomerate having a coating layer containing a flowable carbonaceous material is used on the surface of the core containing iron oxide and a carbonaceous reducing agent. However, there is the biggest feature.

The above-mentioned fluid carbon material means a carbon material that exhibits heat softening properties at 350 ° C. to 400 ° C. “Carbon material showing thermal softening properties” means a carbon material having a softening melting point of 350 ° C. to 400 ° C. when the softening melting point of the carbon material is measured by a method specified in ISO 10329 (2009). I mean.

As the carbon material having fluidity, for example, at least one selected from the group consisting of bituminous coal having fluidity, subbituminous coal having fluidity, and brown coal having fluidity is preferably used. It may be used. Among these carbon materials, it is more preferable to use bituminous coal. In addition, although there exists anthracite in a carbon material, anthracite has no fluidity. Therefore, even if the coating layer 2 contains anthracite, a shell-like spherical body is not formed around the granular iron. Therefore, the core part is exposed to the atmospheric gas in the heating furnace, and the reduced iron obtained by heating and reducing the agglomerate and the granular iron obtained by melting and agglomerating the reduced iron are reoxidized.

The average thickness of the coating layer 2 is not particularly limited, but is preferably, for example, more than 0.30 mm. By making the average thickness of the coating layer 2 exceed 0.30 mm, the effect of suppressing reoxidation of granular iron can be further strengthened, and a petal-like outer shell can be formed. Moreover, it acts effectively also to raise the intensity | strength of the coating layer 2 and to raise the intensity | strength of the whole agglomerate. When the average thickness of the coating layer 2 is 0.30 mm or less, the strength of the coating layer 2 is low, and the shell-like spherical body (that is, petal-like coke) formed by heating the coating layer 2 is also used. Since the thickness is reduced, the oxidation is consumed as the heating time elapses, and it is difficult to maintain the shape until the granular iron is melted and aggregated. Therefore, the average thickness of the coating layer 2 is more preferably 0.50 mm or more, still more preferably 0.70 mm or more, and particularly preferably 1.00 mm or more. The upper limit of the average thickness of the coating layer 2 is not particularly limited, but if it becomes too thick, the amount of carbon material used increases, so the amount of iron contained in the entire agglomerate decreases and productivity decreases. Moreover, it is useless also economically. Therefore, the average thickness of the coating layer 2 is preferably 2.00 mm or less, more preferably 1.80 mm or less, and still more preferably 1.50 mm or less.

The thickness of the coating layer 2 may be measured by observing the cross section of the agglomerate with an optical microscope.

The agglomerates that characterize the production method of the present invention have been described above.

Next, the method for producing granular iron according to the present invention will be described.

The method for producing granular iron according to the present invention includes:
A step of agglomerating a mixture containing iron oxide and a carbonaceous reducing agent to form a nucleus (hereinafter sometimes referred to as a nucleus formation step);
On the surface of the obtained core part, a step of forming a coating layer containing a carbon material having fluidity (hereinafter sometimes referred to as a surface coating step);
The obtained agglomerate is charged on the hearth of a moving bed heating furnace and heated to reduce and melt iron oxide in the agglomerate (hereinafter sometimes referred to as a reductive melting step);
A process of discharging and collecting the obtained granular iron outside the furnace (hereinafter sometimes referred to as a recovery process)
Are included in this order.

[Nucleus formation process]
In the core part forming step, a mixture containing iron oxide and a carbonaceous reducing agent is agglomerated to produce a core part of the agglomerate.

As the iron oxide, specifically, iron oxide sources such as iron ore, iron sand, iron-making dust, non-ferrous refining residue, and iron-making waste can be used.

As the carbonaceous reducing agent, a carbon-containing reducing agent such as coal or coke can be used. When coal is used, coal having fluidity may be used or coal having no fluidity may be used.

The above mixture may further contain a flux. The flux has a role of adjusting the melting point and fluidity of the final slag by fusing with the gangue in the iron oxide source and the ash in the carbonaceous reducing agent.

As the flux, for example, CaO supply material, MgO supply material, Al ₂ O ₃ supply material, SiO ₂ supply material, fluorite (CaF ₂ ) and the like can be used. As said CaO supply substance, for example, at least one selected from the group consisting of CaO (quick lime), Ca (OH) ₂ (slaked lime), CaCO ₃ (limestone), and CaMg (CO ₃ ) ₂ (dolomite) is used. be able to. As the MgO supply substance, for example, at least one selected from the group consisting of CaMg (CO ₃ ) ₂ (dolomite), MgO powder, Mg-containing substance extracted from natural ore or seawater, and MgCO ₃ is blended. Also good. Examples of the Al ₂ O ₃ supply substance include Al ₂ O ₃ powder, bauxite, boehmite, gibbsite, and diaspore. As the SiO ₂ supply substance, for example, SiO ₂ powder or silica sand can be used.

The above mixture may further contain a binder as a component other than iron oxide, carbonaceous reducing agent, and flux.

As the binder, for example, a polysaccharide such as corn starch or starch such as wheat flour can be used.

In the following, flux may be referred to as an additive.

The iron oxide, the carbonaceous reducing agent, and the additive and binder to be blended as necessary may be mixed using a rotating container type mixer, a fixed container type mixer, or the like.

¡The mixture obtained with the above mixer is agglomerated to produce the core of the agglomerate. The average diameter of the core is not particularly limited, but it is recommended to be, for example, 18 to 22 mm.

As the first granulator used when the mixture is agglomerated, for example, a dish granulator, a cylindrical granulator, a twin roll briquette molding machine, an extruder, or the like can be used.

The shape of the core is not particularly limited, and may be, for example, a pellet shape or a briquette shape.

[Surface coating process]
In the surface coating step, a coating layer containing a flowable carbonaceous material is formed on the surface of the core portion obtained in the core portion forming step.

In forming the coating layer, a binder may be included in addition to the carbon material having fluidity. As the binder, those exemplified above can be used.

The kind of the binder contained in the coating layer and the kind of binder contained in the core may be the same or different.

As the second granulator used when forming a coating layer containing a carbon material having fluidity on the surface of the core part, for example, a dish-type granulator or a cylindrical granulator may be used. it can.

The same type of the first granulator and the second granulator may be used, or different types may be used.

The size of the agglomerate in which a coating layer containing a fluid carbon material is formed on the surface of the core is not particularly limited, but the maximum particle size is preferably 50 mm or less. If the particle size of the agglomerate is excessively increased, the granulation efficiency is deteriorated. Moreover, when the agglomerate becomes too large, heat transfer to the lower part of the agglomerate becomes worse and productivity is lowered. In addition, the lower limit of the particle size of the agglomerate is about 5 mm.

The above agglomerates may also be dried by heating in a heating furnace in the reduction melting process described later, but it is recommended to dry before the reduction melting process. Moreover, after granulating the core part, the coating layer may be formed after drying once, but it is preferable to dry after forming the coating layer on the surface of the core part.

[Reduction melting process]
In the reduction melting step, the agglomerate obtained in the surface coating step is charged on the hearth of the moving bed type heating furnace and heated to reduce, melt, and reduce the iron oxide in the agglomerate. Manufactures granular iron made of iron.

The moving bed type heating furnace is a heating furnace in which the hearth moves in the furnace like a belt conveyor, and examples thereof include a rotary hearth furnace and a tunnel furnace. In the rotary hearth furnace, the outer shape of the hearth is designed to be circular or donut shape so that the start point and end point of the hearth are in the same position, and are included in the agglomerate charged on the hearth Iron oxide is heated and reduced during one round of the furnace to produce reduced iron, and subsequently melted and aggregated to produce granular iron and slag. Accordingly, the rotary hearth furnace is provided with charging means for charging the agglomerate into the furnace on the most upstream side in the rotation direction, and with discharging means on the most downstream side in the rotation direction. Since the most downstream side is a rotating structure, the most downstream side is actually immediately upstream of the charging means. The tunnel furnace is a heating furnace in which the hearth moves in the furnace in a linear direction.

The agglomerate is preferably heated at 1350 ° C. or higher. When the heating temperature is lower than 1350 ° C., reduced iron and slag are difficult to melt, and high productivity may not be obtained. Therefore, the heating temperature is preferably 1350 ° C. or higher, more preferably 1400 ° C. or higher. However, when the heating temperature exceeds 1550 ° C., the exhaust gas temperature becomes high, so the exhaust gas treatment facility becomes large and the equipment cost increases. Accordingly, the heating temperature is preferably 1550 ° C. or lower, more preferably 1500 ° C. or lower.

It is preferable to charge the agglomerate so as to form one layer on the hearth. When two or more layers of agglomerates are laminated on the hearth, the agglomerates in the lower layer are not sufficiently heated, and reduction and melting become insufficient, making it difficult to produce granular iron. In addition, 1 layer means that the agglomerate is not laminated | stacked on the vertical direction with respect to a hearth, and there may be a space | gap in the horizontal direction of an agglomerate. That is, the agglomerates need not be densely packed. Moreover, although agglomerates may overlap partially, partial overlap does not negate the effect of the present invention.

Prior to charging the agglomerate onto the hearth, it is preferable to lay a carbonaceous reducing agent on the hearth as a flooring material. By laying the floor covering, the hearth can be protected.

The particle size of the flooring material is preferably 3 mm or less so that the agglomerate and the melt thereof do not sink. The lower limit of the particle size of the floor covering is preferably 0.5 mm or more so as not to be blown off by the burner combustion gas.

[Recovery process]
In the recovery step, the granular iron obtained in the reduction melting step is discharged out of the furnace, and the granular iron is recovered.

In addition, when discharging the granular iron to the outside of the furnace, by-product slag and flooring materials are included in addition to the granular iron. For example, sieving or magnetic separation separator is used outside the furnace. The granular iron can be recovered.

In the production method of the present invention, it is possible to produce granular iron having a C content of 2.5% by mass or more. Moreover, in the manufacturing method of this invention, it becomes possible to manufacture granular iron whose S amount is 0.120 mass% or less.

This application claims the benefit of priority based on Japanese Patent Application No. 2013-198980 filed on September 25, 2013. The entire contents of the specification of Japanese Patent Application No. 2013-198980 are incorporated herein by reference.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited by the following examples, and may be implemented with modifications within a range that can meet the above and the gist described below. Of course, these are all possible and are included in the technical scope of the present invention.

[Experiment 1]
In this experimental example, an agglomerate having a coating layer containing a carbon material having fluidity on the surface and an agglomerate not having the coating layer are prepared, and these are heated in a heating furnace. It was investigated whether reoxidation of the obtained granular iron was suppressed.

First, an agglomerate containing iron oxide and a carbonaceous reducing agent was produced.

As the iron oxide, iron ores having the composition shown in Table 1 below were used. In Table 1, T.W. Fe means total iron. The iron ore used was crushed so that the particle size of 44 μm or less was 67% by mass.

As the carbonaceous reducing agent, carbonaceous materials having the composition shown in Table 2 below were used. In Table 2, T.W. C is all carbon, F.I. C means fixed carbon. As the carbon material, a material pulverized so that a particle size of 75 μm or less was about 55% by mass was used.

The mixture containing the iron ore and the carbon material was further blended with a binder, an additive, and an appropriate amount of water, and these were agglomerated by a first granulator and granulated into raw pellets serving as a core. As the binder, flour was used. As additives, limestone, dolomite, and fluorite were used. A dish granulator was used as the first granulator. The average diameter of the raw pellets was 21 mm. The blending ratio of iron ore, carbonaceous material, binder, and additive is shown in Table 3 below.

A part of the obtained raw pellets was charged into a dryer and heated at 160 ° C. to 180 ° C. for about 1.0 hour to remove the adhering water, thereby producing spherical dry pellets.

On the other hand, a part of the obtained raw pellet was not dried, and a coating layer containing a fluid carbon material was formed on the surface thereof. As the charcoal material having fluidity, after preparing bituminous coal having fluidity and charging the raw pellets into the second granulator, a mixture of bituminous coal and a small amount of binder (wheat flour) is supplied. A coating layer was formed on the surface of the core. A dish granulator was used as the second granulator. The raw pellet obtained by forming a coating layer on the surface of the core was cut, and the cross section was observed with an optical microscope, and it was confirmed that the average thickness of the coating layer was 1.0 mm. Next, the raw pellets having a coating layer formed on the surface are charged into a dryer and heated at 160 ° C. to 180 ° C. for about 1.0 hour to remove adhering water, and spherical dry pellets (ie, agglomerates) ) Was manufactured.

Next, the spherical dry pellets without the coating layer and the spherical dry pellets with the coating layer are charged in a heating furnace (experimental furnace) maintained at about 1450 ° C. and heated to dry. The iron oxide in the pellet was reduced and melted.

The atmosphere in the heating furnace was made to be a highly oxidizing atmosphere by simulating an actual machine. Specifically, the oxidizing gas is represented by carbon dioxide, and a mixed gas atmosphere containing 40% by volume of carbon dioxide and 60% by volume of nitrogen was used. As a result, when the dried pellets were charged into a heating furnace, the coating layer expanded, and the carbonaceous material contained in the coating layer was coke around the core to form a petal-like outer shell. This petal-shaped outer shell acted as a windbreak wall that prevented atmospheric gas from contacting the core.

After reducing and melting iron oxide in a heating furnace, the obtained granular iron was discharged out of the furnace to recover the granular iron. At this time, slag produced as a by-product during the production of granular iron was also collected. The component composition of the obtained granular iron and slag is shown in Table 4 below.

Further, in Table 4 below, the ratio (sulfur distribution ratio) of the S amount (S) contained in the slag to the S amount [S] contained in the granular iron was calculated and shown together.

Based on Table 4, it can be considered as follows.

(No coating layer)
When the coating layer was not formed, as shown in Table 4 below, the amount of FeO in the slag increased to 6.53 mass%. As a result, the sulfur distribution ratio was 1.56, the amount of S contained in the granular iron was 0.171% by mass, and the quality of the granular iron could not be improved.

The reason why the amount of FeO in the slag has increased is considered as follows. That is, in the solid reduction phase, dry pellets that do not form a coating layer generate reduced iron from the top, but part of them are re-oxidized (Fe + CO ₂ = FeO + CO) by the oxidizing gas in the atmosphere. The dissolved FeO is dissolved in the molten slag to produce a high FeO-containing molten slag. Thereafter, a melt-reduction reaction is involved in the melt-aggregation period, and as a result, a reaction (decarburization reaction) between FeO in the slag and [C] in the molten granular iron is caused, and a severe slag forming phenomenon occurs. Since the decarburization reaction is an endothermic reaction, heat transfer to iron is significantly delayed, and the reaction time is greatly extended. In addition, the formed slag covers the semi-molten iron in the course of agglomeration and inhibits heat radiation from the upper part. This also significantly delays heat transfer to the iron and greatly increases the reaction time. Eventually, molten granular iron and molten slag are formed, but the slag is greatly foamed, and FeO contained in the slag is still maintained at a high value. It became 171 mass%. Moreover, [C] in the granular iron to produce | generate was less than 2.5 mass% made into a target, and was 2.49 mass%. Therefore, the quality of the granular iron used as a product is remarkably deteriorated. In addition, due to intense slag forming, the temperature rise of the molten granular iron is hindered, and it does not agglomerate within the prescribed reaction time, forming irregular shaped granular iron incorporating a part of slag at a high ratio, In particular, the value of the product granular iron is significantly reduced.

Here, (1) in FIG. 6 shows a drawing substitute photograph of the granular iron after completion of melting and aggregation. Moreover, the drawing substitute photograph which image | photographed the collect | recovered granular iron is shown to (2) of FIG. Moreover, the drawing substitute photograph which image | photographed the collect | recovered slag is shown to (3) of FIG.

In the present experimental example, since the reaction time (that is, the residence time in the furnace) was sufficiently secured, the recovered granular iron was separated into granular iron and slag as shown in (2) of FIG. I understand that However, in an actual machine, it is difficult to ensure a sufficient residence time in the furnace from the viewpoint of productivity, and the fact is that it must be carried out of the furnace before the aggregation is completely completed. Therefore, further deterioration of the granular iron shape and partial slag and metal separation are insufficiently discharged to the outside of the furnace, and it is inevitable that the quality of the product granular iron and the yield will be reduced.

(With coating layer)
When the dry pellets on which the coating layer is formed are charged into the heating reaction field, the carbonaceous material contained in the coating layer is rapidly coked. At this time, a large crack was generated in the coating layer, but the coating layer was not peeled and dropped, and as shown in FIG. 2, a very characteristic phenomenon of forming a coke wall and wrapping the core was confirmed. The coke wall advances the reduction reaction of iron oxide contained in the core part, and the upper part is released while being gradually oxidized and consumed by the atmospheric gas (C + CO ₂ = 2CO, C + H ₂ O = CO + H ₂ ). It has been found that there may be petals. Furthermore, when the solid reduction is completed, the granular iron generated inside the core and other oxides aggregate while melting at the bottom in the petal-like coke wall, and are separated into molten granular iron and molten slag, The reaction is complete.

In this way, the petal-shaped coke wall plays a very significant role in protecting the core from the oxidizing atmosphere gas, and the core is formed by the atmospheric gas throughout the entire period from the solid reduction phase to the melting and aggregation phase. Remarkable differences were confirmed as compared with the reaction behavior of conventional dry pellets in which the coating layer was not formed, such as reoxidation was significantly suppressed and the reaction was completed.

Here, (1) in FIG. 7 shows a drawing-substituting photograph in which the state after melting and aggregation is completed is photographed. Moreover, the drawing substitute photograph which image | photographed the collect | recovered granular iron is shown to (2) of FIG. In addition, FIG. 7 (3) shows a drawing-substituting photograph in which the collected slag is photographed.

As a result, according to the method of the present invention, as shown in (2) and (3) of FIG. 7, substantially the same shape of granular iron is obtained, and the separability from the recovered slag is also improved. . Moreover, as shown in Table 4, the amount of FeO contained in the slag is 0.29% by mass, indicating that reoxidation of the granular iron is suppressed. Moreover, the sulfur distribution ratio was 14.64, and the amount of S contained in the granular iron could be reduced to 0.059% by mass.

[Experiment 2]
In this experimental example, an agglomerate with a different thickness of the coating layer formed on the surface of the core is manufactured, and this is heated in a heating furnace to check whether reoxidation of the obtained granular iron is suppressed. It was.

First, according to the procedure of Experimental Example 1 above, raw pellets having a coating layer formed on the surface of the core by changing the thickness of the coating layer were manufactured. The core portion where the coating layer was formed was cut, and the cross section was observed with an optical microscope to confirm the thickness of the coating layer. As a result, the average thickness of the coating layer was 0.30 to 2.00 mm.

The raw pellets obtained by forming a coating layer on the surface of the core part are charged into a dryer, heated at 160 ° C. to 180 ° C. for about 1.0 hour to remove adhering water, and spherical dried pellets ( That is, it was set as the agglomerate.

Next, the spherical dry pellets were charged in a heating furnace (experimental furnace) maintained at about 1450 ° C. and heated to reduce and melt the iron oxide in the dry pellets. The atmosphere in the heating furnace was made to be a highly oxidizing atmosphere by simulating an actual machine. Specifically, a mixed gas atmosphere containing 40% by volume of carbon dioxide and 60% by volume of nitrogen was used. As a result, when the dried pellets were charged into a heating furnace, the coating layer expanded, and the carbonaceous material contained in the coating layer was coke around the core to form a petal-like outer shell. The height of the petal-like outer shell was different for each sample, but all acted as a wind barrier preventing atmospheric gas from contacting the core.

After reducing and melting iron oxide in a heating furnace, the obtained granular iron was discharged out of the furnace to recover the granular iron. At this time, slag produced as a by-product during the production of granular iron was also collected. The component composition of the obtained granular iron and slag is shown in Table 5 below.

On the other hand, in Table 5 below, as a comparative example, raw pellets with no coating layer formed on the surface were charged into a dryer as they were and dried under the same conditions as when the coating layer was formed on the surface, and dried in a spherical shape. Pellets were produced.

The obtained spherical dry pellets were heated under the same conditions as when the coating layer was formed on the surface, and the iron oxide in the dry pellets was reduced and melted. The component composition of the obtained granular iron and slag is shown in Table 5 below.

Also, in Table 5 below, the ratio (sulfur distribution ratio) of the S amount (S) contained in the slag to the S amount [S] contained in the granular iron was calculated and shown together.

Based on Table 5 below, it can be considered as follows.

No. No. 8 does not form a coating layer on the surface of the core part, so it cannot prevent reoxidation of granular iron obtained by reduction, and the amount of FeO contained in the slag increases to 6.53% by mass. The distribution ratio was as small as 1.56. As a result, the amount of S contained in the granular iron was as high as 0.171% by mass, and the quality of the granular iron could not be improved.

On the other hand, No. In Nos. 1 to 7, since a coating layer was formed on the surface of the core, reduced iron and granular iron obtained by reducing iron oxide contained in the agglomerate can be prevented from being re-oxidized in the heating furnace. The amount of FeO contained in the steel was reduced to 0.18 to 2.23 mass%, and the sulfur distribution ratio was increased to 41.64 to 2.96. As a result, the amount of S contained in the granular iron was as low as 0.022 to 0.139% by mass, and the quality of the granular iron could be improved. Further, as is apparent from Table 5, it can be seen that as the thickness of the coating layer increases, the amount of FeO contained in the slag decreases and the sulfur distribution ratio tends to increase. Therefore, it can be seen that the amount of S contained in the granular iron can be reduced as the thickness of the coating layer is increased. In particular, no. For 1 to 6, it was possible to suppress the amount of S contained in the granular iron to 0.120% by mass or less.

On the other hand, No. with no coating layer formed on the surface of the core. In No. 8, the amount of carbon contained in the granular iron was a low value of 2.49% by mass, but No. 8 in which a coating layer was formed on the surface of the core part. In Nos. 1 to 7, the amount of carbon contained in the granular iron is as high as 2.65 to 3.52% by mass, and it can be seen that the quality of the granular iron can be improved by forming a coating layer on the surface of the core.

It has been found that the higher the average thickness of the coating layer, the higher the height of the petal-like outer shell formed after the heat reduction treatment.

FIG. 8 is a schematic diagram showing the height of the petal-like wall surface that is formed while the agglomerate is heated and the granular iron is obtained when the thickness of the coating layer is changed. Show. (1) in FIG. 8 shows a case where the average thickness of the coating layer is, for example, 1.30 to 2.00 mm. (2) in FIG. 8 shows a case where the average thickness of the coating layer is, for example, 0.80 to 1.20 mm. (3) in FIG. 8 shows a case where the average thickness of the coating layer is, for example, 0.60 to 0.80 mm. (4) of FIG. 8 shows a case where the average thickness of the coating layer is, for example, more than 0.30 mm and 0.50 mm or less. In FIG. 8, 2 shows a coating layer, 6 shows granular iron, and 7 shows slag.

In addition, No. shown in Table 5 FIG. 9 (1) shows a drawing-substituting photograph taken immediately after the heat reduction treatment of 4. No. shown in Table 5 FIG. 9 (2) shows a drawing-substituting photograph taken immediately after the heat reduction treatment of 5. No. shown in Table 5 FIG. 9 (3) shows a drawing-substituting photograph taken immediately after heat reduction treatment of 6.

Also, No. When the average thickness of the coating layer shown in FIG. 7 was 0.30 mm, small-scale slag foaming occurred. When the average thickness of the coating layer shown in FIG. 6 was 0.50 mm, no slag foaming was observed. On the other hand, no. When a coating layer was not formed on the surface of the core shown in FIG. 8, extremely severe slag forming occurred.

[Experiment 3]
In this experimental example, as the carbon material to be blended in the coating layer formed on the surface of the core part, an agglomerate is produced using a material having no fluidity, and this is heated in a heating furnace, and the obtained granular material It was investigated whether iron reoxidation was suppressed.

First, according to the procedure of Experimental Example 1, raw pellets having a coating layer having an average thickness of 0.50 mm were manufactured on the surface of the core. At this time, anthracite coal was used as a charcoal material having no fluidity instead of the bituminous coal having fluidity. The component composition of the anthracite coal is shown in Table 6 below.

Next, the raw pellets having a coating layer formed on the surface are charged into a dryer and heated at 160 ° C. to 180 ° C. for about 1.0 hour to remove adhering water, and spherical dry pellets (ie, agglomerates) ).

The atmosphere in the heating furnace was made to be a highly oxidizing atmosphere by simulating an actual machine. Specifically, a mixed gas atmosphere containing 40% by volume of carbon dioxide and 60% by volume of nitrogen was used.

As a result, when the dried pellets were charged into a heating furnace, the coating layer expanded, but cracked like a tortoiseshell and deposited on the core as thin fragments, and no petal-like outer shell was formed by coke. The debris deposited on the core part fell to the periphery of the core part as time passed, and the top part of the core part was exposed to the atmospheric gas.

After reducing and melting iron oxide in a heating furnace, the obtained granular iron was discharged out of the furnace to recover the granular iron. At this time, slag produced as a by-product during the production of granular iron was also collected. The composition of the obtained granular iron and slag is shown in Table 7 below.

Further, in Table 7 below, the ratio (sulfur distribution ratio) of the S amount (S) contained in the slag to the S amount [S] contained in the granular iron was calculated and shown together.

Based on Table 7, it can be considered as follows. Even when a coating layer is formed on the surface of the core, if the carbonaceous material blended in the coating layer does not have fluidity, reduced iron obtained by heating and reducing the agglomerate, It can be seen that reoxidation of granular iron obtained by melting and agglomerating reduced iron cannot be prevented, and the amount of FeO contained in slag cannot be reduced. As a result, it is understood that the sulfur distribution ratio is reduced, the amount of sulfur contained in the granular iron is increased, and the quality cannot be improved.

1 Core 2 Covering Layer 3 Agglomerate 4 Reduced Iron 6 Granular Iron 7 Slag

Claims

An agglomerate containing iron oxide and a carbonaceous reducing agent is charged on the hearth of a moving bed type heating furnace and heated, and the iron oxide in the agglomerate is reduced and melted. A method for producing granular iron that is discharged outside the furnace and collected.
The said agglomerate has the coating layer containing the carbonaceous material which has fluidity | liquidity on the surface, The manufacturing method of the granular iron characterized by the above-mentioned.
The production method according to claim 1, wherein the carbon material is at least one selected from the group consisting of bituminous coal, subbituminous coal, and lignite.
The manufacturing method according to claim 1, wherein an average thickness of the coating layer is more than 0.30 mm.
The agglomerates are
After agglomerating the mixture containing iron oxide and carbonaceous reducing agent in the first granulator to form the core,
The manufacturing method according to claim 1, wherein a coating layer containing a fluid carbon material is formed on the surface of the obtained core by a second granulator.
The manufacturing method according to claim 1, wherein the top of the coating layer does not become lower than the top of the granular iron while the agglomerate is heated.
The manufacturing method according to claim 1, wherein the coating layer becomes a shell-like coke while the agglomerate is heated.
The manufacturing method according to claim 1, wherein the agglomerates are charged in a single layer on the hearth.
The manufacturing method according to claim 1, wherein a carbonaceous reducing agent is laid on the hearth prior to charging the agglomerate onto the hearth.
The manufacturing method according to claim 1, wherein the granular iron has a C content of 2.5% by mass or more.
The manufacturing method according to claim 1, wherein the granular iron has an S content of 0.120% by mass or less.