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WO2018194165A1 - Method for smelting metal oxide - Google Patents

Method for smelting metal oxide Download PDF

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Publication number
WO2018194165A1
WO2018194165A1 PCT/JP2018/016342 JP2018016342W WO2018194165A1 WO 2018194165 A1 WO2018194165 A1 WO 2018194165A1 JP 2018016342 W JP2018016342 W JP 2018016342W WO 2018194165 A1 WO2018194165 A1 WO 2018194165A1
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WO
WIPO (PCT)
Prior art keywords
mixture
reduction
flooring material
particles
metal oxide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2018/016342
Other languages
French (fr)
Japanese (ja)
Inventor
井関 隆士
幸弘 合田
純一 小林
岡田 修二
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sumitomo Metal Mining Co Ltd
Original Assignee
Sumitomo Metal Mining Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sumitomo Metal Mining Co Ltd filed Critical Sumitomo Metal Mining Co Ltd
Priority to PH1/2019/502358A priority Critical patent/PH12019502358B1/en
Priority to AU2018254139A priority patent/AU2018254139B2/en
Priority to JP2019513706A priority patent/JP6809603B2/en
Publication of WO2018194165A1 publication Critical patent/WO2018194165A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00Obtaining nickel or cobalt
    • C22B23/02Obtaining nickel or cobalt by dry processes
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B5/00General methods of reducing to metals
    • C22B5/02Dry methods smelting of sulfides or formation of mattes
    • C22B5/10Dry methods smelting of sulfides or formation of mattes by solid carbonaceous reducing agents
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C33/00Making ferrous alloys
    • C22C33/04Making ferrous alloys by melting
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00Preliminary treatment of ores or scrap
    • C22B1/14Agglomerating; Briquetting; Binding; Granulating
    • C22B1/24Binding; Briquetting ; Granulating
    • C22B1/242Binding; Briquetting ; Granulating with binders

Definitions

  • the present invention relates to a metal oxide smelting method, for example, a smelting method of obtaining a reduced product by reducing nickel oxide ore or the like as a raw material with a carbonaceous reducing agent.
  • limonite or saprolite which is a kind of metal oxide ore
  • dry smelting method to produce nickel matte using smelting furnace, rotary kiln or moving hearth furnace HPAL a dry smelting method for producing ferronickel, which is an alloy of iron and nickel
  • a hydrometallurgical method for obtaining nickel cobalt mixed sulfide (mixed sulfide) by adding a high-pressure acid leaching sulfiding agent using an autoclave Processes are known.
  • the raw material nickel oxide ore is crushed to an appropriate size to advance the reaction. Then, the process of forming a lump is performed as a pretreatment.
  • a nickel oxide ore when it is made into a lump from powder or fine particles, the nickel oxide ore and other components, for example, a reducing agent such as a binder or coke are mixed to form a mixture. Further, after performing moisture adjustment and the like, it is inserted into a lump manufacturing machine, for example, a lump or a lump called a pellet or briquette with a diameter of about 10 mm to 30 mm (hereinafter collectively referred to as “pellet”). ).
  • the pellet needs to have a certain degree of air permeability in order to “fly” the contained moisture.
  • the composition of the resulting reduced product becomes non-uniform, resulting in inconveniences such as metal dispersion or uneven distribution. It is important to maintain a uniform temperature as much as possible when the reduction treatment is performed.
  • an agglomerate containing iron oxide as a metal oxide and a carbonaceous reducing agent is supplied onto a hearth of a moving bed type reductive melting furnace, heated, reduced and melted, and then obtained granules.
  • the internal temperature in the first half of the furnace for solid reduction of iron oxide in the agglomerate is 1300 to 1450 ° C.
  • the reduced iron in the agglomerate is reduced.
  • the maximum temperature of the agglomerate to the hearth when the in-furnace temperature in the latter half region of the carburizing, melting and agglomerating furnace is 1400 to 1550 ° C.
  • the distance between the agglomerates spread on the hearth is 0
  • the agglomerated floor density on the hearth is 0.5 or more and 0.8 or less.
  • Patent Document 1 According to such a method of Patent Document 1, it is described that the productivity of granular metallic iron can be improved by controlling together with the agglomerated bed density and the average diameter. As this patent document 1 shows, productivity of granular metal iron can be improved by controlling the bed density and average diameter of an agglomerate.
  • Patent Document 1 is a technique relating to the reaction on the outer surface of the agglomerate.
  • the reduction reaction is a reaction inside the agglomerate. Therefore, in the method of Patent Document 1, it is difficult to control the reduction reaction in the agglomerate.
  • the process using the so-called total melting method in which all raw materials are melted and reduced has a big problem in terms of operation cost.
  • the nickel oxide ore described above it is necessary to heat to a high temperature of 1500 ° C. or higher. In order to obtain such a high temperature, a large energy cost is required, and the furnace used at such a high temperature is easily damaged, so that the repair cost also increases.
  • the target nickel is contained only about 1% in the raw material nickel oxide ore. Therefore, it is not necessary to recover the iron component in excess of the stoichiometric amount necessary for reacting with nickel to form ferronickel, but to melt even a large amount of unnecessary components. Is significantly inefficient.
  • a normal fixed-bed furnace has a structure in which refractory bricks are placed on a frame made of cast iron or the like.
  • the hearth and the furnace wall are less than the fixed bed in order to reduce the power required for rotation.
  • a lighter and thinner structure is employed.
  • a hearth material also called “floor material” is laid on the hearth to protect the hearth from the reaction between the treated material and the hearth and the treated material being seized on the hearth. Measures are taken.
  • coal or coke as the flooring material. Since these also act as reducing agents at the same time, they are not suitable when it is necessary to accurately control and maintain the reducing state in the furnace. In addition, at high temperatures, the effect as a flooring material disappears by reacting with the atmospheric gas and the processed material, making it difficult to use repeatedly and increasing the cost.
  • the present invention has been proposed in view of such circumstances.
  • a metal oxide such as nickel oxide ore containing nickel oxide or the like is used as a raw material, and reduced by a carbonaceous reducing agent to obtain a reduced product.
  • a method capable of obtaining a high-quality reduced product with high efficiency is provided.
  • the present inventors have made extensive studies to solve the above-described problems. As a result, a specific flooring material is used or a flooring material is laid on the hearth in a specific arrangement, and a metal oxide is reduced on the flooring material with a carbonaceous reducing agent to obtain a reduced product. Thus, it was found that an efficient smelting treatment can be performed, and the present invention has been completed. Specifically, the present invention provides the following.
  • a first invention of the present invention is a metal oxide smelting method for reducing a mixture obtained by mixing a metal oxide and a carbonaceous reducing agent in a reduction furnace, comprising alumina, A metal oxide smelting method in which the mixture is heated and reduced on a floor covering composed of one or more materials selected from alumina cement, magnesia, magnesia cement, zirconia, zirconia cement and mullite. .
  • the flooring material is composed of particles of the material (flooring material particles) and is obtained from the following formulas (1) and (2).
  • This is a metal oxide smelting method in which the average floor covering volume ratio is 3% or more and 85% or less.
  • Average floor covering volume ratio total floor covering volume ratio of 300 floor covering particles / 300 (1)
  • Floor covering volume ratio (volume of floor covering particles / volume of sphere having diameter of maximum particle length of floor covering particles) ⁇ 100 (2)
  • a fourth invention of the present invention is a metal oxide smelting method for reducing a mixture obtained by mixing a metal oxide and a carbonaceous reducing agent in a reduction furnace, and having a specific surface area On a floor covering composed of particles (floor covering particles) having an average maximum particle length of not less than 15.0 ⁇ m and not more than 2000 ⁇ m in a range of 0.001 ⁇ m ⁇ 1 to 3.0 ⁇ m ⁇ 1.
  • This is a method for smelting metal oxides by heating and reducing.
  • the flooring material particles are one or more materials selected from alumina, alumina cement, magnesia, magnesia cement, zirconia, zirconia cement and mullite. This is a method for smelting a metal oxide.
  • a sixth invention of the present invention is a metal oxide smelting method for reducing a mixture obtained by mixing a metal oxide and a carbonaceous reducing agent in a reduction furnace, wherein the reduction A flooring material is laid on the hearth of the furnace, the flooring material is composed of particles (flooring material particles), and the number of flooring material particles having a maximum particle length of 50.0 ⁇ m or less contained in the flooring material is It is 1% or more and 40% or less with respect to the total number of flooring material particles contained in the flooring material, and the flooring material particles have an average maximum particle length of 40.0 ⁇ m or more and 1050 ⁇ m determined by the following formula (3).
  • a seventh invention of the present invention is a metal oxide smelting method for reducing a mixture obtained by mixing a metal oxide and a carbonaceous reducing agent in a reduction furnace, Laying flooring material on the hearth of the reduction furnace, A metal oxide smelting method in which the mixture is placed on the floor covering material so as to be 50% or less of the area of the hearth when viewed in plan, and heated and reduced.
  • the eighth invention of the present invention is the method for smelting a metal oxide according to the seventh invention, wherein the mixture has any one of a spherical shape, a cubic shape, and a rectangular parallelepiped shape.
  • a ninth invention of the present invention is a metal oxide smelting method according to any one of the first to eighth inventions, wherein the reduction temperature is 1200 ° C. or higher and 1450 ° C. or lower.
  • a tenth aspect of the present invention is the method for smelting a metal oxide according to any one of the first to ninth aspects, wherein the metal oxide is nickel oxide ore.
  • the eleventh invention of the present invention is a metal oxide smelting method according to any one of the first to tenth inventions, wherein the reduced product contains ferronickel.
  • the metal oxide smelting method according to the present invention is a smelting method in which a metal oxide is used as a raw material to perform a reduction treatment at a high temperature with a carbonaceous reducing agent to obtain a reduced product.
  • a metal oxide is used as a raw material to perform a reduction treatment at a high temperature with a carbonaceous reducing agent to obtain a reduced product.
  • nickel oxide ore containing nickel oxide, iron oxide, etc. as a metal oxide is used as a raw material, and the nickel is prioritized at a high temperature by a carbonaceous reducing agent with respect to the smelting raw material.
  • this metal oxide smelting method uses a specific floor covering material or lays a floor covering material on a hearth in a specific arrangement, and the metal oxide is carbonaceous on the floor covering material. It is characterized by being reduced by a reducing agent, and has four embodiments as specific embodiments.
  • a metal oxide and a carbonaceous reducing agent are formed on a floor covering made of one or more materials selected from alumina, alumina cement, magnesia, magnesia cement, zirconia, zirconia cement, and mullite. The mixture obtained by mixing is reduced.
  • the metal It is characterized in that a mixture obtained by mixing an oxide and a carbonaceous reducing agent is reduced.
  • the particles when reducing the mixture obtained by mixing the metal oxide and the carbonaceous reducing agent in the reducing furnace, the particles are composed of particles and have a maximum particle length of 50.0 ⁇ m or less.
  • the number of particles is 1% or more and 40% or less with respect to the total number of particles in the flooring material, and the average maximum particle length is 40.0 ⁇ m or more and 1050 ⁇ m or less.
  • the metal oxide is reduced with the carbonaceous reducing agent in the main furnace.
  • a floor covering material is laid on the hearth of the reduction furnace, and the mixture is placed on the floor covering material so that it becomes 50% or less of the area of the hearth when viewed in plan. It is arranged and reduced.
  • the metal contained in the metal oxide can be effectively metallized, and an efficient smelting process can be performed.
  • Nickel oxide ore which is a smelting raw material, contains at least nickel oxide.
  • ferronickel iron-nickel alloy
  • nickel oxide contained in the raw material can be manufactured.
  • the present invention is not limited to nickel oxide ore as a metal oxide, and the smelting method is not limited to a method for producing ferronickel from nickel oxide ore containing nickel oxide or the like. Various changes can be made without departing from the scope of the present invention.
  • Nickel oxide ore smelting method is made by mixing and kneading nickel oxide ore, which is a smelting raw material, with a carbonaceous reducing agent or the like to form a mixture and subjecting the mixture to a reduction treatment.
  • ferronickel, which is a metal, and slag are produced as reduction products.
  • the ferronickel which is a metal can be collect
  • FIG. 1 is a process diagram showing an example of the flow of a nickel oxide ore smelting method.
  • this nickel oxide ore smelting method comprises mixing treatment step S1 in which nickel oxide ore and a material such as a carbonaceous reducing agent are mixed to obtain a mixture, and the resulting mixture is agglomerated or
  • a reduction pre-treatment process S2 that fills and molds a predetermined container, a reduction process S3 that reduces the mixture at a predetermined temperature (reduction temperature), and a metal from a mixture that includes the metal and slag generated by the reduction process.
  • Separating step S4 for separating and collecting.
  • the mixing treatment step S1 is a step of obtaining a mixture by mixing raw material powders containing nickel oxide ore. Specifically, in the mixing treatment step S1, nickel oxide ore which is a smelting raw material, iron source such as iron ore, flux component, binder, carbonaceous reducing agent, etc., for example, a particle size of 0.1 mm to 0.8 mm About a raw material powder is mixed at a predetermined ratio to obtain a mixture.
  • the nickel oxide ore which is a smelting raw material ore, is not particularly limited, and limonite or saprolite ore can be used.
  • the iron source supplies iron necessary for reacting with nickel in nickel oxide ore to form ferronickel.
  • the iron source for example, iron ore having an iron grade of about 50% or more, hematite obtained by wet smelting of nickel oxide ore, or the like can be used.
  • Table 1 below shows an example of the composition (wt%) of nickel oxide ore and iron ore as raw materials.
  • a composition of a raw material it is not limited to this.
  • binder examples include bentonite, polysaccharides, resins, water glass, and dehydrated cake.
  • flux component examples include calcium oxide, calcium hydroxide, calcium carbonate, silicon dioxide and the like.
  • this carbonaceous reducing agent has a magnitude
  • the mixing amount of the carbonaceous reducing agent for example, the chemical equivalent required to reduce the total amount of nickel oxide contained in the formed mixture to nickel metal and the ferric oxide contained in the pellets as metal
  • the carbon content is preferably 5% by mass to 60% by mass It is possible to adjust the ratio so as to be a ratio of carbon amount of 10% by mass to 40% by mass.
  • the mixing amount of the carbonaceous reducing agent is such that the amount of carbon is 5% by mass or more with respect to 100% of the total value of chemical equivalents, whereby the reducibility of nickel can be further increased and the productivity can be increased.
  • the amount of carbon is 5% by mass or more with respect to 100% of the total value of chemical equivalents, whereby the reducibility of nickel can be further increased and the productivity can be increased.
  • by reducing the amount of carbon to 60% by mass or less it is possible to suppress the reduction reaction from proceeding excessively, to suppress an increase in the reduction amount of iron and the accompanying decrease in nickel quality in ferronickel, The quality in the obtained ferronickel alloy can be further improved.
  • a shell (metal shell) generated by a metal component can be uniformly generated on the surface of the raw material in the shape of pellets or the like. More preferable in terms of productivity and quality.
  • pellet refers to a lump obtained by molding a mixture obtained by mixing at least the oxide ore and the carbonaceous reducing agent, and may be simply referred to as “mixture”.
  • a mixture is obtained by uniformly mixing the raw material powder containing the nickel oxide ore as described above.
  • kneading may be performed simultaneously, or kneading may be performed after mixing.
  • the contact area between the raw materials is increased and the voids are reduced, so that a reduction reaction is easily caused and a uniform reaction can be achieved.
  • the reaction time of the reduction reaction can be shortened, and quality variation is eliminated. As a result, it is possible to process with high productivity and to manufacture high quality ferronickel.
  • the raw material powder after the raw material powder is kneaded, it may be extruded using an extruder.
  • an extruder by extruding with an extruder, a much higher kneading effect can be obtained, the contact area between the raw material powders can be increased, and the voids can be reduced. Thereby, high quality ferronickel can be produced efficiently.
  • the pre-reduction process step S2 is a step in which the mixture obtained in the mixing step S1 is agglomerated into a mass or filled into a container and molded. That is, in this pre-reduction charging treatment step S2, the mixture obtained by mixing the raw material powders can be easily put into a furnace used in the reduction treatment step S3 described later, and the reduction reaction can be efficiently performed. Mold.
  • the mixture is molded (granulated) into a lump. Specifically, a predetermined amount of moisture necessary for agglomeration is added to the obtained mixture, and for example, an agglomerate production apparatus (such as a tumbling granulator, a compression molding machine, an extrusion molding machine, etc.) And the like (hereinafter also referred to as “pellets”).
  • an agglomerate production apparatus such as a tumbling granulator, a compression molding machine, an extrusion molding machine, etc.
  • pellets agglomerate production apparatus
  • the shape of the pellet is not particularly limited, and may be a spherical shape, a cubic shape, a rectangular parallelepiped shape, or the like.
  • a spherical pellet is preferable because the reduction reaction easily proceeds relatively uniformly.
  • it is a cube shape and a rectangular parallelepiped pellet, it can be stably mounted on the floor covering material laid on the hearth, and handling property improves.
  • the size of the lump to be pelletized is not particularly limited.
  • the size of the pellets charged into the smelting furnace to be used can be about 10 mm to 30 mm. Details of the reduction step will be described later.
  • the mixture can be filled into a predetermined container while kneading with an extruder or the like.
  • the mixture filled in the container is preferably pressed and hardened.
  • the shape of the mixture filled in the container is not particularly limited, but is preferably, for example, spherical, rectangular parallelepiped, cubic or cylindrical.
  • the size is not particularly limited, for example, if it is spherical, it is preferable that the diameter is approximately 500 mm or less.
  • the vertical and horizontal inner dimensions are 500 mm or less.
  • the raw material powder is mixed in the mixing treatment step S1 and the mixture agglomerated in the reduction charging pretreatment step S2 or the mixture filled in the container and molded is predetermined in the reduction furnace.
  • Reduce and heat at the reduction temperature of And a smelting reaction advances by the reduction
  • the flooring material a material composed of one or more materials selected from alumina, alumina cement, magnesia, magnesia cement, zirconia, zirconia cement and mullite is used.
  • a material composed of one or more materials selected from alumina, alumina cement, magnesia, magnesia cement, zirconia, zirconia cement and mullite is used.
  • FIG. 2 is a process diagram showing the process executed in the reduction process S3.
  • the reduction treatment step S3 includes a drying step S31 for drying the mixture, a preheating step S32 for preheating the dried mixture, a reduction step S33 for reducing the mixture, and cooling the obtained reduction product. Cooling step S35. Moreover, it has the temperature holding process S34 which hold
  • the process in the reduction step S33 is performed using a reduction furnace.
  • the reduction furnace for example, a mobile hearth furnace or a rotary hearth furnace can be used.
  • temperature holding process S34 which hold
  • at least the process in reduction process S33 and the process in temperature holding process S34 are performed within one reducing furnace.
  • the temperature in the reducing furnace can be maintained at a high temperature, so that the temperature can be raised or lowered at each treatment in each process. There is no need to do so and the energy cost can be reduced. From this, it is possible to continuously and stably manufacture ferronickel with good quality with high productivity.
  • drying process S31 a drying process is performed with respect to the mixture obtained by mixing raw material powder.
  • the purpose of this drying step S31 is mainly to remove water and crystal water in the mixture.
  • the mixture obtained in the mixing treatment step S1 contains a lot of moisture and the like, and when rapidly heated to a high temperature such as the reduction temperature during the reduction treatment, the moisture is vaporized, expanded and agglomerated at once.
  • the mixture cracks, and in some cases, ruptures into pieces, making it difficult to perform uniform reduction treatment. Therefore, prior to the reduction treatment, the mixture is subjected to a drying treatment to remove moisture, thereby preventing the destruction of pellets and the like.
  • the drying process in drying process S31 is performed in the form connected to a reduction furnace.
  • it can be considered to provide an area (drying area) for performing a drying process in the reduction furnace, in such a case, the drying process in the drying area becomes rate-limiting, and the process in the reduction process S33 and the temperature holding process are performed. There is a possibility of affecting the processing in S34.
  • FIG. 3 shows a configuration example of a rotary hearth furnace 1 which is an example of a reduction furnace and a drying chamber 20 connected to the rotary hearth furnace 1.
  • the drying chamber 20 can be designed completely different from the steps such as preheating, reduction, and cooling described later, and desirable drying treatment, preheat treatment, reduction treatment, It becomes easy to perform each cooling process.
  • the drying chamber 20 may be designed to have a long overall length, or the mixture in the drying chamber 20 What is necessary is just to design so that a conveyance speed may become slow.
  • the drying treatment in the drying chamber 20 for example, the solid content in the mixture can be about 70% by weight and the water content can be about 30% by weight.
  • the drying method is not particularly limited, but can be performed by blowing hot air on the mixture conveyed in the drying chamber 20.
  • the drying temperature is not particularly limited, but from the viewpoint of preventing the reduction reaction from starting, it is preferably 500 ° C. or lower, and it is preferable to uniformly dry at the temperature of 500 ° C. or lower.
  • Table 2 below shows an example of the composition (parts by weight) of the solid content in the mixture after the drying treatment.
  • the composition of the mixture is not limited to this.
  • preheating process S32 the mixture after water
  • the mixture When the mixture is charged into a reduction furnace and heated to a high reduction temperature, the mixture may break or become powdery due to thermal stress. In addition, the temperature of the mixture may not rise uniformly, causing variations in the reduction reaction, and the quality of the metal produced may vary. For this reason, it is preferable to preheat the mixture to a predetermined temperature after the drying treatment, whereby the destruction of the mixture and variations in the reduction reaction can be suppressed.
  • the preheating process in the preheating step S32 is preferably performed in a processing chamber provided outside the reduction furnace, similarly to the drying process, and is performed in a preheating chamber connected to the reduction furnace.
  • FIG. 3 shows a configuration example of the preheating chamber 30 connected to the rotary hearth furnace 1 which is an example of the reduction furnace.
  • the preheating chamber 30 is provided outside the rotary hearth furnace 1. It is continuously provided from the drying chamber 20 that performs the drying process.
  • the pre-heat treatment in the pre-heating chamber 30 provided outside the rotary hearth furnace 1 the temperature in the rotary hearth furnace 1 for performing the reduction process can be maintained at a high temperature, and the rotary furnace The energy required for reheating in the floor furnace 1 can be greatly reduced.
  • the preheat treatment in the preheating chamber 30 is not particularly limited, but is preferably performed at a preheating temperature of 600 ° C or higher, and more preferably at a preheating temperature of 700 ° C or higher and 1280 ° C or lower.
  • a preheating temperature 600 ° C or higher
  • a preheating temperature 700 ° C or higher and 1280 ° C or lower.
  • the mixture preheated in the preheating step S32 is reduced at a predetermined reduction temperature.
  • the reduction process in the reduction step S33 can be performed using a reduction furnace such as a mobile hearth furnace or a rotary hearth furnace. And a floor covering material is arrange
  • At least one material selected from alumina, alumina cement, magnesia, magnesia cement, zirconia, zirconia cement and mullite as a flooring material.
  • the mixture of nickel oxide ore and carbonaceous reducing agent is placed on the floor covering material and placed on the hearth of the reduction furnace to reduce the nickel oxide ore.
  • the shape of the flooring material is not particularly limited, but for example, it is preferable to use a material composed of particles (flooring material particles).
  • floor material particles By configuring the flooring material with the flooring material particles, the contact area between the mixture and the flooring material becomes appropriate, and the operability when spreading on the hearth and the handling when recovering from the hearth Also excellent.
  • the contact area of a mixture and a flooring material is too large, there exists a possibility that reaction with a mixture and a flooring material may advance. On the other hand, if the contact area is too small, the generated slag or metal may penetrate into the gap between the flooring materials.
  • the average flooring material volume ratio is, for example, preferably 3% or more, more preferably 4% or more, and more preferably 5% or more. More preferably.
  • the average floor covering volume ratio is preferably 85% or less, more preferably 82% or less, and further preferably 80% or less.
  • the “maximum particle length” in the above formula (2) refers to the longest diameter or side of a specific particle. Specifically, if the particles are elliptical, the maximum particle length is the major axis, and if the particles are rectangular parallelepiped, the maximum particle length is a diagonal line. Therefore, in the first embodiment, “a sphere having a diameter of the maximum particle length of the flooring material particles” refers to a sphere that is in contact with the flooring material particles and encloses the flooring material particles.
  • FIG. 4 is a schematic diagram of an irregularly shaped particle and a sphere whose diameter is the maximum particle length.
  • the maximum particle length is determined as shown in FIG.
  • the “maximum particle length” can be measured using a metal microscope.
  • the volume of the flooring material particles can be calculated by measuring the weight because the density of the flooring material is known. In this way, 300 randomly selected flooring material particles are measured, the flooring material volume ratio is obtained, and the average flooring material volume ratio is calculated by Equation (1).
  • the size of the flooring material particles is not particularly limited, but the average maximum particle length is preferably 10 ⁇ m or more, more preferably 15 ⁇ m or more. Preferably, it is 20 ⁇ m or more. On the other hand, the average maximum particle length is preferably 6000 ⁇ m or less, more preferably 5500 ⁇ m or less, and even more preferably 5000 ⁇ m or less. When the average maximum particle length is a flooring material in such a range, the contact area between the mixture placed on the flooring material and the flooring material becomes appropriate.
  • the “average maximum particle length” refers to the average maximum particle length of 300 randomly selected floor covering particles, and is obtained by the following formula (3).
  • Average maximum particle length the sum of the maximum particle lengths of 300 flooring materials / 300 (3)
  • the specific surface area of the bedding material particles is not particularly limited, for example, is preferably 0.001 [mu] m -1 or more, 0.002 .mu.m -1 or More preferably, it is 0.003 ⁇ m ⁇ 1 or more.
  • the specific surface area for example, is preferably 3.0 [mu] m -1 or less, more preferably 2.5 [mu] m -1 or less, more preferably 2.0 .mu.m -1 or less.
  • the “specific surface area” can be measured using a general specific surface area measuring apparatus.
  • the placement ratio of the mixture with respect to the hearth is not particularly limited. For example, it is preferable to arrange the mixture so that it becomes 1% or more of the area of the hearth when viewed in plan, It is more preferable to arrange the mixture so as to achieve the above, and it is even more preferable to arrange the mixture so as to be 2% or more.
  • the mixture is preferably arranged so as to be 50% or less of the area of the hearth, and more preferably, the mixture is arranged so as to be 45% or less. It is more preferable to arrange the mixture so as to be not more than%, and it is particularly preferable to arrange the mixture so as to be not more than 40%.
  • the specific surface area is at 0.001 [mu] m -1 or more 3.0 [mu] m -1 or less, and an average maximum particle length of more than 15.0 .mu.m 2000 .mu.m
  • the following flooring material flooring material particles
  • a mixture of nickel oxide ore and carbonaceous reducing agent is placed on the flooring material to reduce the nickel oxide ore. I do.
  • the flooring particles have a specific surface area of 0.001 ⁇ m ⁇ 1 to 3.0 ⁇ m ⁇ 1 and an average maximum particle length of 15.0 ⁇ m to 2000 ⁇ m.
  • a flooring material composed of particles and having a specific surface area and an average maximum particle length in such ranges, the contact area between the mixture and the flooring material becomes appropriate.
  • the contact area of a mixture and a flooring material is too large, there exists a possibility that reaction of both may advance.
  • the contact area is too small, the generated slag or metal may penetrate into the gap between the flooring materials.
  • the “specific surface area” can be measured using a general specific surface area measuring apparatus.
  • maximum particle length refers to the longest diameter or side of a specific particle. Specifically, if the particles are elliptical, the maximum particle length is the major axis, and if the particles are rectangular parallelepiped, the maximum particle length is a diagonal line.
  • FIG. 5 is a schematic diagram showing the maximum particle length of irregular shaped particles. In the case of irregularly shaped particles, the maximum particle length is determined as shown in FIG. This “maximum particle length” can be measured using a metallographic microscope.
  • the “average maximum particle length” is an average value of the maximum particle lengths of 300 randomly selected floor covering particles.
  • the bedding material particles are not particularly limited, but it is preferable to use those composed of one or more materials selected from alumina, alumina cement, magnesia, magnesia cement, zirconia, zirconia cement and mullite.
  • alumina alumina cement
  • magnesia magnesia cement
  • zirconia zirconia cement
  • mullite a material selected from alumina, alumina cement, magnesia, magnesia cement, zirconia, zirconia cement and mullite.
  • the specific surface area of the bedding material particles is preferably 0.002 .mu.m -1 or more, and more preferably 0.003 .mu.m -1 or more.
  • the specific surface area is preferably 2.5 [mu] m -1 or less, more preferably 2.0 .mu.m -1 or less.
  • the average maximum particle length of the flooring particles is preferably 17.0 ⁇ m or more, and more preferably 20.0 ⁇ m or more.
  • the average maximum particle length of the flooring particles is preferably 1500 ⁇ m or less, more preferably 1200 ⁇ m or less, and even more preferably 1000 ⁇ m or less.
  • the placement ratio of the mixture with respect to the hearth is not particularly limited. For example, it is preferable to arrange the mixture so that it becomes 1% or more of the area of the hearth when viewed in plan, It is more preferable to arrange the mixture so as to achieve the above, and it is even more preferable to arrange the mixture so as to be 2% or more.
  • the mixture is preferably arranged so as to be 50% or less of the area of the hearth, and more preferably, the mixture is arranged so as to be 45% or less. It is more preferable to arrange the mixture so as to be not more than%, and it is particularly preferable to arrange the mixture so as to be not more than 40%.
  • the floor covering material is composed of particles (floor covering material particles), and the maximum particle length contained in the floor covering material is 50.0 ⁇ m or less.
  • a reduction furnace in which the number of flooring particles is 1% or more and 40% or less with respect to the total number of flooring particles contained in the flooring material, and the average maximum particle length is 40.0 ⁇ m or more and 1050 ⁇ m or less.
  • the mixture of nickel oxide ore and carbonaceous reductant is placed on the floor covering material to reduce the nickel oxide ore.
  • maximum particle length refers to the longest side or diameter of a specific particle. Specifically, for example, if the particle is elliptical, the maximum particle length is a long diameter, and if the particle is a rectangular parallelepiped, the maximum particle length is a diagonal line.
  • FIG. 5 is a schematic diagram showing the maximum particle length of irregular shaped particles. In the case of irregularly shaped particles, the maximum particle length is determined as shown in FIG. This “maximum particle length” can be measured using a metallographic microscope.
  • the number of flooring material particles having a maximum particle length of 50.0 ⁇ m or less contained in the flooring material is 1 with respect to the total number of flooring material particles contained in the flooring material. % Or more and 40% or less is used.
  • the number of flooring material particles having a maximum particle length of 50.0 ⁇ m or less included in the flooring material is not particularly limited as long as it is included in the above-described range.
  • the total flooring included in the flooring material It is preferably 1.2% or more, more preferably 1.5% or more, still more preferably 1.7% or more, and particularly preferably 2% or more with respect to the number of material particles. preferable.
  • the number of flooring material particles having a maximum particle length of 50.0 ⁇ m or less contained in the flooring material is, for example, 37% or less with respect to the total number of flooring material particles contained in the flooring material. It is preferably 35% or less, more preferably 32% or less, and particularly preferably 30% or less.
  • the flooring material one having an average maximum particle length of 40.0 ⁇ m or more and 1050 ⁇ m or less is used.
  • the average maximum particle length is preferably 42.0 ⁇ m or more, more preferably 45.0 ⁇ m or more, further preferably 47.0 ⁇ m or more, and particularly preferably 50.0 ⁇ m or more.
  • the average maximum particle length is preferably 1030 ⁇ m or less, and more preferably 1000 ⁇ m or less.
  • the specific surface area of the bedding material particles is not particularly limited, for example, is preferably 0.001 [mu] m -1 or more, more preferably 0.002 .mu.m -1 or more, is 0.003 .mu.m -1 or More preferably.
  • the specific surface area for example, is preferably 3.0 [mu] m -1 or less, more preferably 2.5 [mu] m -1 or less, more preferably 2.0 .mu.m -1 or less.
  • the “specific surface area” can be measured using a general specific surface area measuring apparatus.
  • the floor covering material is not particularly limited, but it is preferable to use a material composed of one or more materials selected from alumina, alumina cement, magnesia, magnesia cement, zirconia, zirconia cement or mullite.
  • a material composed of one or more materials selected from alumina, alumina cement, magnesia, magnesia cement, zirconia, zirconia cement or mullite By using such a flooring material, the reaction between the mixture and the hearth and the reaction between the mixture and the flooring material can be further suppressed, and high-quality ferronickel can be produced. Further, the flooring material can be reused, and as a result, the cost of smelting can be reduced.
  • the placement ratio of the mixture with respect to the hearth is not particularly limited. For example, it is preferable to arrange the mixture so that it becomes 1% or more of the area of the hearth when viewed in plan, It is more preferable to arrange the mixture so as to achieve the above, and it is even more preferable to arrange the mixture so as to be 2% or more.
  • the mixture is preferably arranged so as to be 50% or less of the area of the hearth, and more preferably, the mixture is arranged so as to be 45% or less. It is more preferable to arrange the mixture so as to be not more than%, and it is particularly preferable to arrange the mixture so as to be not more than 40%.
  • the floor covering material is laid on the hearth of the reduction furnace, and when the hearth floor is viewed in plan on the floor covering material, the area of the hearth floor is reduced.
  • the mixture is arranged so as to be 50% or less, and nickel oxide ore is reduced.
  • the reaction between the mixture and the hearth and the reaction between the mixture and the flooring material are suppressed by placing the mixture on the flooring material at a specific placement ratio (placement area ratio) and performing a reduction treatment.
  • High quality ferronickel can be produced and can be recovered effectively.
  • the cost of smelting can be reduced by reusing the flooring material.
  • the mixture is arranged on the hearth of the reduction furnace so that the area of the hearth becomes 50% or less when viewed in plan.
  • the contact area between the mixture and the flooring material becomes appropriate.
  • reaction of both may advance.
  • the contact area is too small, the generated slag or metal may penetrate into the gap between the flooring materials.
  • the mixture is preferably arranged so as to be 3% or more of the area of the hearth, and the mixture is arranged so as to be 5% or more. It is more preferable.
  • the mixture in the hearth of the reduction furnace, the mixture is preferably arranged to be 45% or less, more preferably the mixture is arranged to be 42% or less, and the mixture is made to be 40% or less. It is further preferable to arrange By arranging the mixture in such an area with respect to the hearth, the contact area between the mixture and the flooring material becomes more appropriate.
  • FIG. 6 is a schematic diagram showing an installation example of a spherical mixture with respect to a flooring material.
  • FIG. 7 is a schematic diagram showing an installation example of a rectangular parallelepiped mixture with respect to the flooring material.
  • it is preferable to install the mixture so that at least a part thereof is embedded on the flooring material.
  • the shape of the flooring material is not particularly limited, but it is preferable to use particles composed of particles (flooring material particles).
  • particles composed of particles as the flooring material, the contact area between the mixture and the flooring material becomes more appropriate, and the operability when laying on the hearth and when recovering from the hearth Excellent handleability.
  • the specific surface area of the bedding material particles is not particularly limited, for example, is preferably 0.001 [mu] m -1 or more, 0.002 .mu.m -1 or More preferably, it is 0.003 ⁇ m ⁇ 1 or more.
  • the specific surface area for example, is preferably 3.0 [mu] m -1 or less, more preferably 2.5 [mu] m -1 or less, more preferably 2.0 .mu.m -1 or less.
  • the “specific surface area” can be measured using a general specific surface area measuring apparatus.
  • the size of the flooring material particles is not particularly limited, for example, the average maximum particle length is preferably 20.0 ⁇ m or more and 1000 ⁇ m or less, More preferably, it is 50.0 ⁇ m or more and 700 ⁇ m or less. When the average maximum particle length of the flooring material is in such a range, the contact area between the mixture and the flooring material becomes more appropriate.
  • maximum particle length refers to the longest side or diameter of a specific particle. Specifically, for example, if the particle is elliptical, the maximum particle length is a long diameter, and if the particle is a rectangular parallelepiped, the maximum particle length is a diagonal line. This “maximum particle length” can be measured using a metallographic microscope. In the fourth embodiment, the “average maximum particle length” is an average value of the maximum particle lengths of 100 randomly selected flooring material particles.
  • the floor covering material is not particularly limited, but it is preferable to use a material composed of one or more materials selected from alumina, alumina cement, magnesia, magnesia cement, zirconia, zirconia cement and mullite.
  • a material composed of one or more materials selected from alumina, alumina cement, magnesia, magnesia cement, zirconia, zirconia cement and mullite By using such a flooring material, the reaction between the mixture and the hearth and the reaction between the mixture and the flooring material can be further suppressed, and high-quality ferronickel can be produced. Further, the flooring material can be reused, and as a result, the cost of smelting can be reduced.
  • nickel oxide which is a metal oxide contained in nickel oxide ore
  • nickel oxide ore is reduced as completely as possible and preferentially to iron, while raw powder together with nickel oxide ore. It is preferable to carry out so-called partial reduction, in which iron oxide derived from iron ore and the like mixed is partially reduced to obtain ferronickel having a target nickel quality.
  • the reduction temperature is not particularly limited, but is preferably in the range of 1200 ° C to 1450 ° C, and more preferably in the range of 1300 ° C to 1400 ° C.
  • a reduction reaction can be caused uniformly and a metal (ferronickel metal) with suppressed quality variation can be generated.
  • a metal ferrronickel metal
  • a desired reduction reaction can be caused in a relatively short time.
  • the slag or metal generated from the mixture may react with the hearth and damage the hearth in a short time.
  • the metal component of a hearth etc. may mix in the mixture or the reduced metal, and there exists a possibility of causing the fall of the quality of the metal obtained.
  • floor covering materials such as coal and coke, are used, there exists a possibility that the slag and metal produced
  • the internal temperature of the reduction chamber in the reduction furnace is raised until the reduction temperature in the above-described range, and the temperature is maintained after the temperature rise.
  • the reduction furnace for example, a mobile hearth furnace or a rotary hearth furnace can be used. According to such a reduction furnace, the metal contained in the metal oxide can be effectively metalized and an efficient smelting treatment can be performed.
  • a rotary hearth furnace will be described with reference to FIG. 3 as an example of a reduction furnace.
  • FIG. 3 is a diagram (plan view) showing a configuration example of a rotary hearth furnace in which the hearth rotates.
  • the rotary hearth furnace 1 has a region 10 in which the hearth rotates, and the region 10 is divided into four, and each constitutes a processing chamber (10a, 10b, 10c, 10d). Yes.
  • all four treatment chambers with reference numerals “10a” to “10d” may be reduction chambers for performing reduction treatment.
  • the processing chambers “10a”, “10b”, and “10c” are set as the reduction chamber, and the processing chamber “10d” is held at the temperature. It can be set as the temperature holding chamber which performs the process in process S34.
  • the cooling step S5 described later is performed after the processing in the reduction step S33, for example, the processing chambers “10a”, “10b”, and “10c” are set as the reduction chamber, and the processing chamber “10d” is set as the cooling step S5. It can be set as the temperature holding chamber which performs the process in.
  • each process that is, between each processing chamber, be partitioned by a partition wall in order to strictly control the reaction temperature and suppress energy loss.
  • the rotary hearth furnace having a structure capable of partitioning the sub-size of each process, the energy loss is suppressed between the process in the reduction process S33 and the process in the temperature holding process S34, as will be described later.
  • the same rotary hearth furnace can be used.
  • the partition wall is of a fixed type, it may be difficult to transport between processes, and particularly to charge and discharge the rotary hearth furnace. It is preferable to have a structure that can be opened and closed to the extent that it does not interfere with.
  • the number of processing chambers formed by dividing the area 10 in which the hearth rotates is not limited to four illustrated in FIG. Further, the number of reduction chambers and the number of temperature holding chambers are not limited to the above-described example, and can be appropriately set according to the processing time and the like.
  • the rotary hearth furnace 1 includes a hearth that rotates and moves on a plane, and the hearth on which the mixture is placed rotates and moves at a predetermined speed, so that each processing chamber (10a, 10a, 10b, 10c, 10d), and processing is performed at the time of the passage.
  • each processing chamber (10a, 10a, 10b, 10c, 10d) is performed at the time of the passage.
  • the arrow on the rotary hearth furnace 1 in FIG. 3 shows the rotation direction of a hearth, it shows the moving direction of a processed material (mixture).
  • the rotary hearth furnace 1 is connected to a drying chamber 20 provided outside the furnace and a preheating chamber 30, and as described above, after the drying treatment is performed on the mixture in the drying chamber 20.
  • the dried mixture moves to the preheating chamber 30 and is preheated, and the preheated mixture is sequentially transferred into the rotary hearth furnace 1.
  • the rotary hearth furnace 1 is connected to a cooling chamber 40 provided outside the furnace, and the reduced product obtained through the reduction chamber or the temperature holding chamber (10d) is cooled in the cooling chamber 40. (Cooling step S35 described later).
  • the metal component in the reduced product is small in the state obtained by the reduction treatment, for example, when it is a bulk metal of about 200 ⁇ m or less, the metal and slag are separated in the subsequent separation step S4. Will become difficult. For this reason, if necessary, the reduced product is kept at a high temperature, so that the metal having a specific gravity larger than that of the slag in the reduced product is settled and aggregated to coarsen the metal.
  • the reduced product holding temperature in the temperature holding step S34 is preferably in the high temperature range of 1300 ° C to 1500 ° C.
  • the metal component in the reduced product can be efficiently precipitated to form a coarse metal.
  • the holding temperature is lower than 1300 ° C., a large part of the reduced product becomes a solid phase, so that it takes time even when the metal component does not settle or settles.
  • the holding temperature exceeds 1500 ° C., the reaction between the obtained reduced product and the flooring material proceeds and the reduced product may not be recovered, and the furnace may be damaged.
  • the treatment in the temperature holding step S34 is performed continuously following the reduction treatment in the rotary hearth furnace 1 used in the reduction step S33. That is, as described with reference to FIG. 3, in the rotary hearth furnace 1, for example, the processing chambers “10a”, “10b”, and “10c” are used as the reduction chambers, and the processing chamber “10d” is used in the temperature holding step S34. A temperature holding chamber for processing is used, and the reduced product obtained through the reduction chambers (10a, 10b, 10c) is held in a predetermined temperature range in the temperature holding chamber (10d).
  • the metal component in the reduction product is efficiently settled by continuously performing the process of maintaining the reduction product obtained through the reduction treatment at a predetermined temperature using the rotary hearth furnace 1. Can be coarsened.
  • the process in the reduction process S33 and the process in the temperature holding process S34 are continuously performed using the rotary hearth furnace 1 instead of separate furnaces, so that heat loss between the processes is reduced and efficient. Enable operation.
  • Cooling step S35 the reduction product obtained through the reduction step S33 or the reduction product after being held at a high temperature for a predetermined time in the temperature holding step S34 is separated and recovered in the subsequent separation step S4. Cool down to a temperature where you can.
  • the cooling step S35 is a step of cooling the reduction product obtained as described above, it is preferably performed in a cooling chamber connected to the outside of the rotary hearth furnace 1.
  • FIG. 3 shows a configuration example of the cooling chamber 40 connected to the rotary hearth furnace 1.
  • the cooling chamber 40 is provided outside the rotary hearth furnace 1.
  • the temperature in the cooling step S35 (hereinafter also referred to as “recovery temperature”) is a temperature at which the reduced product can be handled substantially as a solid, and is preferably as high as possible.
  • the recovery temperature is preferably 600 ° C. or higher.
  • the energy required for reheating can be greatly reduced, and efficient smelting treatment can be performed at low cost.
  • the temperature difference in the rotary hearth furnace 1 the thermal stress applied to the hearth, the furnace wall, etc. can be reduced, and the life of the rotary hearth furnace 1 can be greatly extended. In addition, problems during operation can be greatly reduced.
  • Separation process S4 isolate
  • the obtained metal phase and slag phase can be easily separated because of poor wettability, and for example, when a large mixture is dropped with a predetermined drop, or when sieving By giving an impact such as giving a predetermined vibration, the metal phase and the slag phase can be easily separated from the mixture.
  • the metal phase can be recovered and made into a ferronickel product.
  • Example 1 (Mixing process) Mix nickel oxide ore as raw material oxide ore, iron ore, silica sand and limestone as flux components, binder and coal as carbonaceous reducing agent using a mixer while adding appropriate amount of water. To obtain a mixture.
  • the carbonaceous reducing agent is 30% in terms of carbon when the total value of chemical equivalents required for reducing nickel oxide and iron oxide (Fe 2 O 3 ) to metal without excess or deficiency is 100%. In an amount corresponding to.
  • the mixture obtained by mixing with a mixer was kneaded with a twin-screw kneader.
  • the rotary hearth furnace 1 includes a drying chamber 20 for drying pellets, a preheating chamber 30 provided continuously to the drying chamber 20, and a processing chamber in the furnace, as shown in FIG. 3. What connected with the cooling chamber 40 which cools the reduced material obtained through 10a-10d was used. In Example 1, the processing chamber 10d was used as a cooling chamber.
  • the pellet sample was placed in the drying chamber 20 connected to the outside of the rotary hearth furnace 1 and dried.
  • hot air 250 ° C. to 350 ° C. is blown onto the pellets in a nitrogen atmosphere that does not substantially contain oxygen so that the pellets have a solid content of about 70% by weight and water content of about 30% by weight. Went by. Table 3 below shows the solid content composition (excluding carbon) of the pellets after the drying treatment.
  • the pellets after the drying treatment are transferred to a preheating chamber 30 continuously provided in the drying chamber 20, and the temperature in the preheating chamber 30 is maintained in a range of 700 ° C. or higher and 1280 ° C. or lower, so Heat treatment was performed.
  • the pellets after the pre-heat treatment were transferred into the rotary hearth furnace 1 and subjected to reduction treatment and temperature holding treatment.
  • the rotary hearth furnace 1 the region 10 in which the hearth rotates and moves is divided into four, and four processing chambers are provided, and all the four processing chambers 10a to 10d perform reduction processing. The room.
  • the reduced product obtained through the reduction treatment was transferred to a cooling chamber connected to the rotary hearth furnace 1 and quickly cooled to room temperature while flowing nitrogen and taken out into the atmosphere.
  • the reductant was recovered from the rotary hearth furnace 1 in a form in which the reductant was transferred to the cooling chamber 40, and the reductant was recovered along with a guide installed in the cooling chamber 40.
  • Examples 1-1 to 1-48 a flooring material composed of particles was laid on the hearth, and a pellet of the mixture was placed thereon to perform a reduction treatment.
  • the reduction treatment was performed by placing the pellets directly on the metal hearth. Tables 4 to 6 below show the conditions for the reduction treatment in the reduction steps of Examples 1 to 48 and Comparative Examples 1-1 to 1-3.
  • the average maximum particle length was obtained from the average value of the maximum particle lengths of 300 floor covering particles randomly selected and measured using a metal microscope. Further, the volume of the flooring material is determined by measuring the total weight of 300 particles used to obtain the average value of the maximum particle length and dividing by the density of the material constituting the flooring material. Asked.
  • the nickel quality of the sample taken out was analyzed with an ICP emission spectroscopic analyzer (SHIMAZU S-8100), and the nickel metal ratio and the nickel content in the metal were calculated.
  • the nickel metal ratio was calculated by the following formula (4), and the nickel content in the metal was calculated by the following formula (5).
  • Tables 4 to 6 below show the nickel metal ratio and the nickel content in the metal of the samples obtained in Examples 1-1 to 1-48 and Comparative Examples 1-1 to 1-3.
  • the predetermined flooring material was used, so that the flooring material and the hearth did not react with the sample, and as a result, high quality with less impurities and the like. Of ferronickel could be produced. Further, since the flooring material can be reused, it can be realized at a low cost. Furthermore, since the metal component is large, the metal is likely to become coarse.
  • Example 2 (Mixing process) Mix nickel oxide ore as raw material oxide ore, iron ore, silica sand and limestone as flux components, binder and coal as carbonaceous reducing agent using a mixer while adding appropriate amount of water. To obtain a mixture.
  • the carbonaceous reducing agent is 36% in terms of carbon amount when the total value of chemical equivalents required to reduce nickel oxide and iron oxide (Fe 2 O 3 ) to metal without excess or deficiency is 100%. In an amount corresponding to.
  • the mixture obtained by mixing with a mixer was kneaded with a twin-screw kneader.
  • the rotary hearth furnace 1 includes a drying chamber 20 for drying pellets, a preheating chamber 30 provided continuously to the drying chamber 20, and a processing chamber in the furnace, as shown in FIG. 3. What connected with the cooling chamber 40 which cools the reduced material obtained through 10a-10d was used. In Example 2, the processing chamber 10d was used as a cooling chamber.
  • the pellet sample was placed in the drying chamber 20 connected to the outside of the rotary hearth furnace 1 and dried.
  • hot air 250 ° C. to 350 ° C. is blown onto the pellets in a nitrogen atmosphere that does not substantially contain oxygen so that the pellets have a solid content of about 70% by weight and water content of about 30% by weight. Went by. Table 7 below shows the solid content composition (excluding carbon) of the pellets after the drying treatment.
  • the pellets after the drying treatment are transferred to a preheating chamber 30 continuously provided in the drying chamber 20, and the temperature in the preheating chamber 30 is maintained in a range of 700 ° C. or higher and 1280 ° C. or lower, so Heat treatment was performed.
  • the pellets after the pre-heat treatment were transferred into the rotary hearth furnace 1 and subjected to reduction treatment and temperature holding treatment.
  • the rotary hearth furnace 1 the region 10 in which the hearth rotates and moves is divided into four, and four processing chambers are provided, and all the four processing chambers 10a to 10d perform reduction processing. The room.
  • the reduced product obtained through the reduction treatment was transferred to a cooling chamber connected to the rotary hearth furnace 1 and quickly cooled to room temperature while flowing nitrogen and taken out into the atmosphere.
  • the reductant was recovered from the rotary hearth furnace 1 in a form in which the reductant was transferred to the cooling chamber 40, and the reductant was recovered along with a guide installed in the cooling chamber 40.
  • the specific surface area of the flooring material was measured using a Shimadzu Corporation specific surface area measuring device (Flowsorb III2305).
  • the average maximum particle length was determined from the average value of the maximum particle lengths of 300 floor covering particles randomly selected and measured using a metal microscope. Further, the volume of the flooring material is determined by measuring the total weight of 300 particles used to obtain the average value of the maximum particle length and dividing by the density of the material constituting the flooring material. Asked.
  • Nickel metalization rate amount of Ni metalized in the reduction treatment input pellet / (total amount of Ni in the reduction treatment input pellet) ⁇ 100 (%)
  • Nickel content in metal amount of Ni metalized in the reduction treatment input pellet / (total amount of metal Ni and Fe in the reduction treatment input pellet) ⁇ 100 (%) (5)
  • Ni metal recovery rate ⁇ recovered Ni amount / (input amount of nickel oxide ore ⁇ Ni content ratio) ⁇ ⁇ 100 (6)
  • Tables 8 to 10 below show the nickel metal ratio, the nickel content in the metal, and the nickel recovery rate of the samples obtained in Examples 2-1 to 2-48 and Comparative Examples 2-1 to 2-12.
  • Examples 2-1 to 2-48 by using a predetermined floor covering material, uniform and stable reduction can be performed. As a result, the Ni metalization rate and the recovery rate are high, High quality ferronickel could be produced for Ni. Moreover, a floor covering material can be used continuously and nickel can be manufactured cheaply. Further, since the Ni content ratio metal component is large, the metal tends to be coarsened.
  • Example 3 (Mixing process) Mix nickel oxide ore as raw material oxide ore, iron ore, silica sand and limestone as flux components, binder and coal as carbonaceous reducing agent using a mixer while adding appropriate amount of water. To obtain a mixture.
  • the carbonaceous reducing agent is 30% in terms of carbon when the total value of chemical equivalents required for reducing nickel oxide and iron oxide (Fe 2 O 3 ) to metal without excess or deficiency is 100%. In an amount corresponding to.
  • the mixture obtained by mixing with a mixer was kneaded with a twin-screw kneader.
  • Examples 3-1 to 3-12, Examples 3-25 to 3-36, Comparative Example 3-1, Comparative Example 3-2, Comparative Example 3-5, and Comparative Example 3-6 were obtained by kneading.
  • the obtained mixture sample was formed into spherical pellets of ⁇ 16 ⁇ 1.5 mm using a pan granulator.
  • the rotary hearth furnace 1 includes a drying chamber 20 for drying pellets, a preheating chamber 30 provided continuously to the drying chamber 20, and a processing chamber in the furnace, as shown in FIG. 3. What connected with the cooling chamber 40 which cools the reduced material obtained through 10a-10d was used. In Example 3, the processing chamber 10d was used as a cooling chamber.
  • the pellet sample was placed in the drying chamber 20 connected to the outside of the rotary hearth furnace 1 and dried.
  • hot air 250 ° C. to 350 ° C. is blown onto the pellets in a nitrogen atmosphere that does not substantially contain oxygen so that the pellets have a solid content of about 70% by weight and water content of about 30% by weight. Went by. Table 11 below shows the solid content composition (excluding carbon) of the pellets after the drying treatment.
  • the pellets after the drying treatment are transferred to a preheating chamber 30 continuously provided in the drying chamber 20, and the temperature in the preheating chamber 30 is maintained in a range of 700 ° C. or higher and 1280 ° C. or lower, so Heat treatment was performed.
  • the pellets after the pre-heat treatment were transferred into the rotary hearth furnace 1 and subjected to reduction treatment and temperature holding treatment.
  • the rotary hearth furnace 1 the region 10 in which the hearth rotates and moves is divided into four, and four processing chambers are provided, and all the four processing chambers 10a to 10d perform reduction processing. The room.
  • the reduced product obtained through the reduction treatment was transferred to a cooling chamber connected to the rotary hearth furnace 1 and quickly cooled to room temperature while flowing nitrogen and taken out into the atmosphere.
  • the reductant was recovered from the rotary hearth furnace 1 in a form in which the reductant was transferred to the cooling chamber 40, and the reductant was recovered along with a guide installed in the cooling chamber 40.
  • the specific surface area of the flooring material was measured using a Shimadzu Corporation specific surface area measuring device (Flowsorb III2305).
  • Flowsorb III2305 Shimadzu Corporation specific surface area measuring device
  • For the average value of the maximum particle length an average value of the maximum particle lengths of 300 flooring material particles randomly selected and measured using a metal microscope was obtained.
  • Nickel metalization rate amount of Ni metalized in the reduction treatment input pellet / (total amount of Ni in the reduction treatment input pellet) ⁇ 100 (%)
  • Nickel content in metal amount of Ni metalized in the reduction treatment input pellet / (total amount of metal Ni and Fe in the reduction treatment input pellet) ⁇ 100 (%) (5)
  • Ni metal recovery rate ⁇ recovered Ni amount / (input amount of nickel oxide ore ⁇ Ni content ratio) ⁇ ⁇ 100 (6)
  • Tables 12 to 14 below show the nickel metal ratio, the nickel content in the metal, and the nickel recovery rate of the samples obtained in Examples 3-1 to 3-48 and Comparative Examples 3-1 to 3-12.
  • Examples 3-1 to 3-48 by using a predetermined floor covering material, uniform and stable reduction can be performed. As a result, the Ni metalization rate and the recovery rate are high, High quality ferronickel could be produced for Ni. Moreover, a floor covering material can be used continuously and nickel can be manufactured cheaply. Further, since the Ni content ratio metal component is large, the metal tends to be coarsened.
  • Example 4 (Mixing process) Mix nickel oxide ore as raw material oxide ore, iron ore, silica sand and limestone as flux components, binder and coal as carbonaceous reducing agent using a mixer while adding appropriate amount of water. To obtain a mixture.
  • the carbonaceous reducing agent is 30% in terms of carbon when the total value of chemical equivalents required for reducing nickel oxide and iron oxide (Fe 2 O 3 ) to metal without excess or deficiency is 100%. In an amount corresponding to.
  • the mixture obtained by mixing with a mixer was kneaded with a twin-screw kneader.
  • Examples 4-1 to 4-12, Examples 4-25 to 4-36, Comparative Example 4-1, Comparative Example 4-2, Comparative Example 4-5 and Comparative Example 4-6 were obtained by kneading.
  • the obtained mixture sample was formed into spherical pellets with a diameter of 15 ⁇ 1.5 mm using a bread granulator.
  • the rotary hearth furnace 1 includes a drying chamber 20 for drying pellets, a preheating chamber 30 provided continuously to the drying chamber 20, and a processing chamber in the furnace, as shown in FIG. 3. What connected with the cooling chamber 40 which cools the reduced material obtained through 10a-10d was used. In Example 4, the processing chamber 10d was used as a cooling chamber.
  • the pellet sample was placed in the drying chamber 20 connected to the outside of the rotary hearth furnace 1 and dried.
  • hot air 250 ° C. to 350 ° C. is blown onto the pellets in a nitrogen atmosphere that does not substantially contain oxygen so that the pellets have a solid content of about 70% by weight and water content of about 30% by weight. Went by. Table 15 below shows the solid content composition (excluding carbon) of the pellets after the drying treatment.
  • the pellets after the drying treatment are transferred to a preheating chamber 30 continuously provided in the drying chamber 20, and the temperature in the preheating chamber 30 is maintained in a range of 700 ° C. or higher and 1280 ° C. or lower, so Heat treatment was performed.
  • the pellets after the pre-heat treatment were transferred into the rotary hearth furnace 1 and subjected to reduction treatment and temperature holding treatment.
  • the rotary hearth furnace 1 the region 10 in which the hearth rotates and moves is divided into four, and four processing chambers are provided, and all the four processing chambers 10a to 10d perform reduction processing. The room.
  • the reduced product obtained through the reduction treatment was transferred to a cooling chamber connected to the rotary hearth furnace 1 and quickly cooled to room temperature while flowing nitrogen and taken out into the atmosphere.
  • the reductant was recovered from the rotary hearth furnace 1 in a form in which the reductant was transferred to the cooling chamber 40, and the reductant was recovered along with a guide installed in the cooling chamber 40.
  • Nickel metalization rate amount of Ni metalized in the reduction treatment input pellet / (total amount of Ni in the reduction treatment input pellet) ⁇ 100 (%)
  • Nickel content in metal amount of Ni metalized in the reduction treatment input pellet / (total amount of metal Ni and Fe in the reduction treatment input pellet) ⁇ 100 (%) (5)
  • Ni metal recovery rate ⁇ recovered Ni amount / (input amount of nickel oxide ore ⁇ Ni content ratio) ⁇ ⁇ 100 (6)
  • Tables 16 to 18 below show the nickel metal ratio, the nickel content in the metal, and the nickel recovery rate of the samples obtained in Examples 4-1 to 4-48 and Comparative Examples 4-1 to 4-8.
  • the mixture was arranged at a specific ratio with respect to the hearth, so that uniform and stable reduction could be performed.
  • the Ni metalization rate and the recovery were achieved.
  • the rate was high and it was possible to produce high quality ferronickel for Ni.
  • a floor covering material can be used continuously and nickel can be manufactured cheaply. Further, since the Ni content ratio metal component is large, the metal tends to be coarsened.

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Abstract

Provided is a smelting method whereby reduction by a carbonaceous reducing agent is performed to obtain a reduced substance using as a raw material a nickel oxide ore or other metal oxide containing oxidized nickel or the like, for example, wherein a high-quality reduced substance can be obtained with high efficiency. The method for smelting a metal oxide pertaining to the present invention comprises reducing a mixture obtained by mixing a metal oxide and a carbonaceous reducing agent in a reducing furnace, wherein the mixture obtained by mixing a metal oxide and a carbonaceous reducing agent is heated and reduced on a floor covering material composed of one or more types of materials selected from alumina, alumina cement, magnesia, magnesia cement, zirconia, zirconia cement, and mullite.

Description

金属酸化物の製錬方法Metal oxide smelting method

 本発明は、金属酸化物の製錬方法に関するものであり、例えば、ニッケル酸化鉱石等を原料として炭素質還元剤により還元することで還元物を得る製錬方法に関する。 The present invention relates to a metal oxide smelting method, for example, a smelting method of obtaining a reduced product by reducing nickel oxide ore or the like as a raw material with a carbonaceous reducing agent.

 金属酸化物の鉱石の一種であるリモナイトあるいはサプロライトと呼ばれるニッケル酸化鉱石の製錬方法として、熔錬炉を使用してニッケルマットを製造する乾式製錬方法、ロータリーキルンあるいは移動炉床炉を使用して鉄とニッケルの合金であるフェロニッケルを製造する乾式製錬方法、オートクレーブを使用して高圧酸浸出し硫化剤を添加してニッケルコバルト混合硫化物(ミックスサルファイド)を得る湿式製錬法であるHPALプロセス等が知られている。 As a smelting method of nickel oxide ore called limonite or saprolite which is a kind of metal oxide ore, dry smelting method to produce nickel matte using smelting furnace, rotary kiln or moving hearth furnace HPAL, a dry smelting method for producing ferronickel, which is an alloy of iron and nickel, and a hydrometallurgical method for obtaining nickel cobalt mixed sulfide (mixed sulfide) by adding a high-pressure acid leaching sulfiding agent using an autoclave Processes are known.

 上述した様々な方法の中で、特に乾式製錬法を用いてニッケル酸化鉱石を還元して製錬する場合、反応を進めさせるために原料のニッケル酸化鉱石を適度な大きさに破砕する等して塊状物化する処理が前処理として行われる。 Among the various methods described above, particularly when nickel oxide ore is reduced and smelted using a dry smelting method, the raw material nickel oxide ore is crushed to an appropriate size to advance the reaction. Then, the process of forming a lump is performed as a pretreatment.

 具体的に、ニッケル酸化鉱石を塊状物化する、すなわち粉や微粒状から塊状にする際には、そのニッケル酸化鉱石と、それ以外の成分、例えばバインダーやコークス等の還元剤と混合して混合物とし、さらに水分調整等を行った後に塊状物製造機に装入して、例えば一辺あるいは直径が10mm~30mm程度の大きさのペレットやブリケットと称せられる塊状物(以下、まとめて単に「ペレット」という)とするのが一般的である。 Specifically, when a nickel oxide ore is agglomerated, that is, when it is made into a lump from powder or fine particles, the nickel oxide ore and other components, for example, a reducing agent such as a binder or coke are mixed to form a mixture. Further, after performing moisture adjustment and the like, it is inserted into a lump manufacturing machine, for example, a lump or a lump called a pellet or briquette with a diameter of about 10 mm to 30 mm (hereinafter collectively referred to as “pellet”). ).

 さて、ペレットには、含有する水分を「飛ばす」ために、ある程度の通気性が必要となる。また、ペレット内で均一に還元が進まないと、得られる還元物の組成が不均一になり、メタルが分散したり偏在したりする等の不都合が生じるため、混合物を均一に混合し、またペレットを還元処理する際には可能な限り均一な温度を維持することが重要となる。 Now, the pellet needs to have a certain degree of air permeability in order to “fly” the contained moisture. In addition, if the reduction does not proceed uniformly in the pellet, the composition of the resulting reduced product becomes non-uniform, resulting in inconveniences such as metal dispersion or uneven distribution. It is important to maintain a uniform temperature as much as possible when the reduction treatment is performed.

 加えて、還元されて生成したフェロニッケルを粗大化させることも重要な技術となる。これは、生成したフェロニッケルが、例えば数10μm~数100μm以下の細かな大きさであった場合、同時に生成するスラグと物理的に分離することが困難となり、フェロニッケルとしての回収率(収率)が大きく低下するためである。 In addition, it is an important technique to coarsen the reduced ferronickel produced. This is because when the produced ferronickel has a fine size of, for example, several tens of μm to several hundred μm, it is difficult to physically separate from the slag produced at the same time, and the recovery rate (yield as ferronickel) ) Is greatly reduced.

 また、製錬コストを如何に低く抑えることができるかについても重要な技術的事項であり、コンパクトな設備で操業できる連続処理が望まれている。 Also, how to keep the smelting cost low is an important technical matter, and continuous processing that can be operated with compact equipment is desired.

 例えば、特許文献1には、金属酸化物としての酸化鉄及び炭素質還元剤を含む塊成物を移動床型還元溶融炉の炉床上に供給して加熱し、還元溶融した後、得られる粒状金属を冷却してから炉外へ排出して回収する方法において、塊成物中の酸化鉄を固体還元する炉の前半領域における炉内温度を1300~1450℃、塊成物中の還元鉄を浸炭、溶融させ、凝集させる炉の後半領域における炉内温度を1400~1550℃とするとともに、炉床上に敷き詰めた塊成物同士の距離を0としたときの塊成物の炉床への最大投影面積率に対し、炉床上に敷き詰めた塊成物の炉床への投影面積率の相対値を敷密度としたとき、炉床上における塊成物の敷密度を0.5以上0.8以下として加熱する際に、平均直径が19.5mm以上32mm以下の塊成物を炉床上に供給する方法が開示されている。 For example, in Patent Document 1, an agglomerate containing iron oxide as a metal oxide and a carbonaceous reducing agent is supplied onto a hearth of a moving bed type reductive melting furnace, heated, reduced and melted, and then obtained granules. In the method of cooling and recovering the metal to the outside of the furnace, the internal temperature in the first half of the furnace for solid reduction of iron oxide in the agglomerate is 1300 to 1450 ° C., and the reduced iron in the agglomerate is reduced. The maximum temperature of the agglomerate to the hearth when the in-furnace temperature in the latter half region of the carburizing, melting and agglomerating furnace is 1400 to 1550 ° C. and the distance between the agglomerates spread on the hearth is 0 With respect to the projected area ratio, when the relative value of the projected area ratio of the agglomerate spread on the hearth to the hearth is defined as the bed density, the agglomerated floor density on the hearth is 0.5 or more and 0.8 or less. When heating as an average diameter of 19.5 mm or more and 32 mm or less The method for supplying agglomerates to the hearth are disclosed.

 このような特許文献1の方法によれば、塊成物の敷密度と平均直径と併せて制御することによって、粒状金属鉄の生産性を向上できることが記載されている。この特許文献1が示すとおり、塊成物の敷密度と平均直径を制御することによって、粒状金属鉄の生産性を向上できる。しかしながら、特許文献1は塊成物の外面での反応に関する技術である。これに対し、還元反応は塊成物内部での反応である。したがって、特許文献1の方法では、塊成物内での還元反応を制御することは困難である。 According to such a method of Patent Document 1, it is described that the productivity of granular metallic iron can be improved by controlling together with the agglomerated bed density and the average diameter. As this patent document 1 shows, productivity of granular metal iron can be improved by controlling the bed density and average diameter of an agglomerate. However, Patent Document 1 is a technique relating to the reaction on the outer surface of the agglomerate. In contrast, the reduction reaction is a reaction inside the agglomerate. Therefore, in the method of Patent Document 1, it is difficult to control the reduction reaction in the agglomerate.

 また、特許文献1のように塊成物の直径を決められた範囲に限定すると、塊成物の製造時の収率が下がり、コスト増加となる問題もある。さらに、塊成物の敷密度が0.5以上0.8以下の範囲は最密に充填された状態でなく、また塊成物を積層している状態でもないので効率は低い。さらに、特許文献1のような移動炉床の炉を用いた場合、連続して操業が行われるために、炉の状態を常に安定して維持することも重要である。 Further, when the diameter of the agglomerate is limited to a predetermined range as in Patent Document 1, there is a problem in that the yield during the production of the agglomerate is lowered and the cost is increased. Further, when the density of the agglomerated material is in the range of 0.5 to 0.8, the efficiency is low because the agglomerated material is not in a close-packed state and is not a state in which the agglomerated material is laminated. Further, when a moving hearth furnace such as that disclosed in Patent Document 1 is used, since the operation is continuously performed, it is also important to constantly maintain the state of the furnace.

 さらに、特許文献1のように、原料全てを熔解して還元するいわゆる全熔解法を用いたプロセスでは、操業コストの面でも大きな問題がある。例えば、上述したニッケル酸化鉱石を完全に熔融するには、1500℃以上もの高温に加熱する必要がある。このような高温を得るためには多大なエネルギーコストがかかり、また、そのような高温で用いる炉が傷みやすくなるので、補修費も増大する。また、目的とするニッケルは、原料のニッケル酸化鉱石中に1%程度しか含有されていない。したがって、ニッケルと反応してフェロニッケルを形成するために必要な化学量論量を超える量の鉄成分は回収する必要がないにもかかわらず、多量の回収不要な成分までも全てを熔融することになり著しく非効率的である。 Furthermore, as in Patent Document 1, the process using the so-called total melting method in which all raw materials are melted and reduced has a big problem in terms of operation cost. For example, in order to completely melt the nickel oxide ore described above, it is necessary to heat to a high temperature of 1500 ° C. or higher. In order to obtain such a high temperature, a large energy cost is required, and the furnace used at such a high temperature is easily damaged, so that the repair cost also increases. The target nickel is contained only about 1% in the raw material nickel oxide ore. Therefore, it is not necessary to recover the iron component in excess of the stoichiometric amount necessary for reacting with nickel to form ferronickel, but to melt even a large amount of unnecessary components. Is significantly inefficient.

 このため、必要なニッケルだけを優先的に還元し、ニッケルよりもはるかに多量に含有される鉄の還元は部分的にしか行わない部分熔解による還元方法(「部分還元法」、あるいはニッケル優先還元法ともいう)が検討されてきた。 For this reason, only the necessary nickel is preferentially reduced and the iron contained in a much larger amount than nickel is reduced only partially. The reduction method by partial melting ("partial reduction method" or nickel preferential reduction). (Also called the law) has been studied.

 しかしながら、このような部分還元法においては原料を完全に熔解せず、半固体状態に維持しながら還元反応を行うため、ニッケルを100%完全に還元しながら、一方で鉄の還元を、ごく一部だけに留めるように反応を制御することは容易でない。このため、原料内での還元に部分的なばらつきが生じ、ニッケル回収率の低下など効率的な操業が困難であった。 However, in such a partial reduction method, since the raw material is not completely melted and the reduction reaction is performed while maintaining a semi-solid state, nickel is completely reduced while iron is reduced only once. It is not easy to control the reaction so that only the part remains. For this reason, the partial dispersion | variation arises in the reduction | restoration within a raw material, and efficient operations, such as a fall of a nickel recovery rate, were difficult.

 ところで、高温で反応を行う還元炉においては、その材質が問題となる。通常の固定床の炉では、鋳鉄等で構成された枠に耐火煉瓦を載せる等の構造を有するが、回転炉床炉では回転に要する動力を低減するために、炉床や炉壁は固定床よりも軽量化された薄い構造を採る場合も多い。このような場合、炉床上に炉敷材(「床敷材」ともいう)を敷き、処理物と炉床とが反応したり、処理物が炉床に焼付いたりしないよう炉床を保護するための対策が採られている。 By the way, the material of the reducing furnace that reacts at a high temperature becomes a problem. A normal fixed-bed furnace has a structure in which refractory bricks are placed on a frame made of cast iron or the like. However, in a rotary hearth furnace, the hearth and the furnace wall are less than the fixed bed in order to reduce the power required for rotation. In many cases, a lighter and thinner structure is employed. In such a case, a hearth material (also called “floor material”) is laid on the hearth to protect the hearth from the reaction between the treated material and the hearth and the treated material being seized on the hearth. Measures are taken.

 従来、この床敷材として、石炭やコークス等を用いることが一般的であった。これらは、同時に還元剤としても働くため、炉内の還元状態を正確に制御、維持することが必要な場合には適さない。また、高温下では雰囲気ガスや処理物と反応して床敷材としての効果が消滅することで、繰り返しの使用等が困難となり、コストが増加する問題もあった。 Conventionally, it has been common to use coal or coke as the flooring material. Since these also act as reducing agents at the same time, they are not suitable when it is necessary to accurately control and maintain the reducing state in the furnace. In addition, at high temperatures, the effect as a flooring material disappears by reacting with the atmospheric gas and the processed material, making it difficult to use repeatedly and increasing the cost.

 このように、金属酸化物を高効率に還元し、高品質な還元物を得ることは容易ではない。 Thus, it is not easy to reduce the metal oxide with high efficiency and obtain a high-quality reduced product.

特開2011-256414号公報JP 2011-256414 A

 本発明は、このような実情に鑑みて提案されたものであり、例えば、酸化ニッケル等を含有するニッケル酸化鉱石等の金属酸化物を原料とし、炭素質還元剤によって還元して還元物を得る製錬方法において、高品質の還元物を高効率に得ることができる方法を提供する。 The present invention has been proposed in view of such circumstances. For example, a metal oxide such as nickel oxide ore containing nickel oxide or the like is used as a raw material, and reduced by a carbonaceous reducing agent to obtain a reduced product. In the smelting method, a method capable of obtaining a high-quality reduced product with high efficiency is provided.

 本発明者らは、上述した課題を解決するために鋭意検討を重ねた。その結果、特定の床敷材を用いるか、特定の配置で床敷材を炉床に敷いて、その床敷材の上で金属酸化物を炭素質還元剤によって還元して還元物を得ることにより、効率的な製錬処理を行うことができることを見出し、本発明を完成するに至った。具体的に、本発明は以下のものを提供する。 The present inventors have made extensive studies to solve the above-described problems. As a result, a specific flooring material is used or a flooring material is laid on the hearth in a specific arrangement, and a metal oxide is reduced on the flooring material with a carbonaceous reducing agent to obtain a reduced product. Thus, it was found that an efficient smelting treatment can be performed, and the present invention has been completed. Specifically, the present invention provides the following.

 (1)本発明の第1の発明は、還元炉内で、金属酸化物と炭素質還元剤とを混合して得られた混合物を還元する金属酸化物の製錬方法であって、アルミナ、アルミナセメント、マグネシア、マグネシアセメント、ジルコニア、ジルコニアセメント及びムライトから選択される1種以上の材料から構成される床敷材上で、前記混合物を加熱し還元する、金属酸化物の製錬方法である。 (1) A first invention of the present invention is a metal oxide smelting method for reducing a mixture obtained by mixing a metal oxide and a carbonaceous reducing agent in a reduction furnace, comprising alumina, A metal oxide smelting method in which the mixture is heated and reduced on a floor covering composed of one or more materials selected from alumina cement, magnesia, magnesia cement, zirconia, zirconia cement and mullite. .

 (2)本発明の第2の発明は、第1の発明において、前記床敷材は、前記材料の粒子(床敷材粒子)から構成され、下記式(1)及び(2)より求められる平均床敷材体積率が3%以上85%以下である、金属酸化物の製錬方法である。
 平均床敷材体積率
 =床敷材粒子300個の床敷材体積率の総和/300  ・・・(1)
 床敷材体積率
 =(床敷材粒子の体積/床敷材粒子の最大粒子長を直径とする球の体積)×100  ・・・(2)
(2) According to a second aspect of the present invention, in the first aspect, the flooring material is composed of particles of the material (flooring material particles) and is obtained from the following formulas (1) and (2). This is a metal oxide smelting method in which the average floor covering volume ratio is 3% or more and 85% or less.
Average floor covering volume ratio = total floor covering volume ratio of 300 floor covering particles / 300 (1)
Floor covering volume ratio = (volume of floor covering particles / volume of sphere having diameter of maximum particle length of floor covering particles) × 100 (2)

 (3)本発明の第3の発明は、第1又は第2の発明において、前記床敷材は、前記材料の粒子(床敷材粒子)から構成され、下記式(3)より求められる平均最大粒子長が10μm以上6000μm以下である、金属酸化物の製錬方法である。
 平均最大粒子長
 =床敷材粒子300個の最大粒子長の総和/300  ・・・(3)
(3) According to a third aspect of the present invention, in the first or second aspect, the flooring material is composed of particles of the material (flooring material particles) and is an average obtained from the following formula (3): This is a metal oxide smelting method having a maximum particle length of 10 μm or more and 6000 μm or less.
Average maximum particle length = sum of maximum particle lengths of 300 flooring particles / 300 (3)

 (4)本発明の第4の発明は、還元炉内で、金属酸化物と炭素質還元剤とを混合して得られた混合物を還元する金属酸化物の製錬方法であって、比表面積が0.001μm-1以上3.0μm-1以下であり、且つ平均最大粒子長が15.0μm以上2000μm以下である粒子(床敷材粒子)から構成される床敷材上で、前記混合物を加熱し還元する、金属酸化物の製錬方法である。 (4) A fourth invention of the present invention is a metal oxide smelting method for reducing a mixture obtained by mixing a metal oxide and a carbonaceous reducing agent in a reduction furnace, and having a specific surface area On a floor covering composed of particles (floor covering particles) having an average maximum particle length of not less than 15.0 μm and not more than 2000 μm in a range of 0.001 μm −1 to 3.0 μm −1. This is a method for smelting metal oxides by heating and reducing.

 (5)本発明の第5の発明は、第4の発明において、前記床敷材粒子は、アルミナ、アルミナセメント、マグネシア、マグネシアセメント、ジルコニア、ジルコニアセメント及びムライトから選択される1種以上の材料から構成される、金属酸化物の製錬方法である。 (5) According to a fifth aspect of the present invention, in the fourth aspect, the flooring material particles are one or more materials selected from alumina, alumina cement, magnesia, magnesia cement, zirconia, zirconia cement and mullite. This is a method for smelting a metal oxide.

 (6)本発明の第6の発明は、還元炉内で、金属酸化物と炭素質還元剤とを混合して得られた混合物を還元する金属酸化物の製錬方法であって、前記還元炉の炉床上に床敷材を敷き、前記床敷材は粒子(床敷材粒子)から構成され、該床敷材に含まれる最大粒子長50.0μm以下の床敷材粒子の数が、該床敷材に含まれる総床敷材粒子の数に対し1%以上40%以下であり、前記床敷材粒子は、下記式(3)により求められる平均最大粒子長が40.0μm以上1050μm以下である、金属酸化物の製錬方法である。
 平均最大粒子長
 =床敷材粒子300個の最大粒子長の総和/300  ・・・(3)
(6) A sixth invention of the present invention is a metal oxide smelting method for reducing a mixture obtained by mixing a metal oxide and a carbonaceous reducing agent in a reduction furnace, wherein the reduction A flooring material is laid on the hearth of the furnace, the flooring material is composed of particles (flooring material particles), and the number of flooring material particles having a maximum particle length of 50.0 μm or less contained in the flooring material is It is 1% or more and 40% or less with respect to the total number of flooring material particles contained in the flooring material, and the flooring material particles have an average maximum particle length of 40.0 μm or more and 1050 μm determined by the following formula (3). The following is a method for smelting a metal oxide.
Average maximum particle length = sum of maximum particle lengths of 300 flooring particles / 300 (3)

 (7)本発明の第7の発明は、還元炉内で、金属酸化物と炭素質還元剤とを混合して得られた混合物を還元する金属酸化物の製錬方法であって、
 前記還元炉の炉床上に床敷材を敷き、
 前記床敷材上に、前記炉床を平面視したときに該炉床の面積の50%以下となるように前記混合物を配置して加熱し還元する、金属酸化物の製錬方法である。
(7) A seventh invention of the present invention is a metal oxide smelting method for reducing a mixture obtained by mixing a metal oxide and a carbonaceous reducing agent in a reduction furnace,
Laying flooring material on the hearth of the reduction furnace,
A metal oxide smelting method in which the mixture is placed on the floor covering material so as to be 50% or less of the area of the hearth when viewed in plan, and heated and reduced.

 (8)本発明の第8の発明は、第7の発明において、前記混合物は、球状、立方体状又は直方体状のいずれかの形状を有する、金属酸化物の製錬方法である。 (8) The eighth invention of the present invention is the method for smelting a metal oxide according to the seventh invention, wherein the mixture has any one of a spherical shape, a cubic shape, and a rectangular parallelepiped shape.

 (9)本発明の第9の発明は、第1乃至第8のいずれかの発明において、還元温度が、1200℃以上1450℃以下である、金属酸化物の製錬方法である。 (9) A ninth invention of the present invention is a metal oxide smelting method according to any one of the first to eighth inventions, wherein the reduction temperature is 1200 ° C. or higher and 1450 ° C. or lower.

 (10)本発明の第10の発明は、第1乃至第9のいずれかの発明において、前記金属酸化物は、ニッケル酸化鉱石である、金属酸化物の製錬方法である。 (10) A tenth aspect of the present invention is the method for smelting a metal oxide according to any one of the first to ninth aspects, wherein the metal oxide is nickel oxide ore.

 (11)本発明の第11の発明は、第1乃至第10のいずれかの発明において、前記還元物は、フェロニッケルを含有する、金属酸化物の製錬方法である。 (11) The eleventh invention of the present invention is a metal oxide smelting method according to any one of the first to tenth inventions, wherein the reduced product contains ferronickel.

 本発明によれば、例えば、酸化ニッケル等を含有するニッケル酸化鉱石等の金属酸化物を原料とし、炭素質還元剤で還元して還元物を得る製錬方法において、高品質の還元物を高効率に得ることができる。 According to the present invention, for example, in a smelting method in which a metal oxide such as nickel oxide ore containing nickel oxide or the like is used as a raw material and reduced with a carbonaceous reducing agent to obtain a reduced product, Can be obtained efficiently.

ニッケル酸化鉱石の製錬方法の流れの一例を示す工程図である。It is process drawing which shows an example of the flow of the smelting method of nickel oxide ore. 還元処理工程にて実行する処理工程を示す工程である。It is a process which shows the process process performed in a reduction process process. 炉床が回転する回転炉床炉の構成例を示す図(平面図)である。It is a figure (plan view) showing an example of composition of a rotary hearth furnace where a hearth rotates. 不定形粒子及びその最大粒子長を直径とする球の模式図である。It is a schematic diagram of an irregular particle and a sphere whose diameter is the maximum particle length. 不定形粒子の最大粒子長を示す模式図である。It is a schematic diagram which shows the maximum particle length of an amorphous particle. 床敷材に対する球状の混合物の設置例を示す模式図である。It is a schematic diagram which shows the example of installation of the spherical mixture with respect to a floor covering material. 床敷材に対する直方体状の混合物の設置例を示す模式図である。It is a schematic diagram which shows the example of installation of the rectangular parallelepiped mixture with respect to a floor covering material.

 ≪1.本発明の概要≫
 本発明に係る金属酸化物の製錬方法は、金属酸化物を原料として、炭素質還元剤により高温下で還元処理を行って還元物を得る製錬方法である。例えば、金属酸化物として、酸化ニッケルや酸化鉄等を含有するニッケル酸化鉱石を原料とし、その製錬原料に対して炭素質還元剤により高温下でニッケルを優先して、また、鉄を部分的に還元することでフェロニッケルを製造する方法が挙げられる。
<< 1. Outline of the present invention >>
The metal oxide smelting method according to the present invention is a smelting method in which a metal oxide is used as a raw material to perform a reduction treatment at a high temperature with a carbonaceous reducing agent to obtain a reduced product. For example, nickel oxide ore containing nickel oxide, iron oxide, etc. as a metal oxide is used as a raw material, and the nickel is prioritized at a high temperature by a carbonaceous reducing agent with respect to the smelting raw material. A method for producing ferronickel by reduction to the above.

 具体的に、この金属酸化物の製錬方法は、特定の床敷材を用いるか、特定の配置で床敷材を炉床に敷いて、その床敷材の上で金属酸化物を炭素質還元剤によって還元することを特徴とするものであり、具体的態様として、4つの態様を有する。第1の態様では、アルミナ、アルミナセメント、マグネシア、マグネシアセメント、ジルコニア、ジルコニアセメント及びムライトから選択される1種以上の材料から構成される床敷材上で、金属酸化物と炭素質還元剤とを混合して得られた混合物を還元することを特徴とする。第2の態様では、比表面積が0.001μm-1以上3.0μm-1以下であり、且つ平均最大粒子長が15.0μm以上2000μm以下である粒子から構成される床敷材上で、金属酸化物と炭素質還元剤とを混合して得られた混合物を還元することを特徴とする。第3の態様では、還元炉内で、金属酸化物と炭素質還元剤とを混合して得られた混合物を還元するに際し、粒子から構成され、最大粒子長50.0μm以下の床敷材粒子の数が、床敷材に含まれる総床敷材粒子数に対し1%以上40%以下であり、平均最大粒子長が40.0μm以上1050μm以下である床敷材粒子を用いることを特徴とする。第4の態様では、還元炉内で、金属酸化物と炭素質還元剤とを混合して得られた混合物を還元するに際し、元炉内で、金属酸化物を炭素質還元剤で還元して還元物を得る製錬処理に際し、還元炉の炉床上に床敷材を敷き、その床敷材上に、炉床を平面視したときに炉床の面積の50%以下となるように混合物を配置して還元することを特徴とする。 Specifically, this metal oxide smelting method uses a specific floor covering material or lays a floor covering material on a hearth in a specific arrangement, and the metal oxide is carbonaceous on the floor covering material. It is characterized by being reduced by a reducing agent, and has four embodiments as specific embodiments. In the first aspect, a metal oxide and a carbonaceous reducing agent are formed on a floor covering made of one or more materials selected from alumina, alumina cement, magnesia, magnesia cement, zirconia, zirconia cement, and mullite. The mixture obtained by mixing is reduced. In a second aspect, and a specific surface area of 0.001 [mu] m -1 or more 3.0 [mu] m -1 or less, and an average maximum particle length on configured bedding material from the particles is less than 2000μm or 15.0μm, the metal It is characterized in that a mixture obtained by mixing an oxide and a carbonaceous reducing agent is reduced. In the third aspect, when reducing the mixture obtained by mixing the metal oxide and the carbonaceous reducing agent in the reducing furnace, the particles are composed of particles and have a maximum particle length of 50.0 μm or less. The number of particles is 1% or more and 40% or less with respect to the total number of particles in the flooring material, and the average maximum particle length is 40.0 μm or more and 1050 μm or less. To do. In the fourth aspect, when reducing the mixture obtained by mixing the metal oxide and the carbonaceous reducing agent in the reduction furnace, the metal oxide is reduced with the carbonaceous reducing agent in the main furnace. In the smelting process to obtain a reduced product, a floor covering material is laid on the hearth of the reduction furnace, and the mixture is placed on the floor covering material so that it becomes 50% or less of the area of the hearth when viewed in plan. It is arranged and reduced.

 このような製錬方法によれば、金属酸化物中に含まれる金属を効果的にメタル化することができ、しかも効率的な製錬処理を行うことができる。 According to such a smelting method, the metal contained in the metal oxide can be effectively metallized, and an efficient smelting process can be performed.

 以下では、本発明の具体的な実施形態(以下、「本実施の形態」という)として、ニッケル酸化鉱石の製錬方法を例に挙げて説明する。製錬原料であるニッケル酸化鉱石は酸化ニッケルを少なくとも含むものであり、このニッケル酸化鉱石の製錬方法では、原料中に含まれる酸化ニッケル等を還元することによってフェロニッケル(鉄-ニッケル合金)を製造することができる。 Hereinafter, as a specific embodiment of the present invention (hereinafter referred to as “the present embodiment”), a method for smelting nickel oxide ore will be described as an example. Nickel oxide ore, which is a smelting raw material, contains at least nickel oxide. In this nickel oxide ore smelting method, ferronickel (iron-nickel alloy) is reduced by reducing nickel oxide contained in the raw material. Can be manufactured.

 なお、本発明は、金属酸化物としてニッケル酸化鉱石に限定されるものではなく、製錬方法としても酸化ニッケル等を含むニッケル酸化鉱石からフェロニッケルを製造する方法に限られるものではない。また、本発明の要旨を変更しない範囲で種々の変更が可能である。 It should be noted that the present invention is not limited to nickel oxide ore as a metal oxide, and the smelting method is not limited to a method for producing ferronickel from nickel oxide ore containing nickel oxide or the like. Various changes can be made without departing from the scope of the present invention.

 ≪2.ニッケル酸化鉱石の製錬方法≫
 本実施の形態に係るニッケル酸化鉱石の製錬方法は、製錬原料であるニッケル酸化鉱石を炭素質還元剤等と混合、混練して混合物を作り、その混合物に対して還元処理を施すことによって、還元物としてメタルであるフェロニッケルとスラグとを生成させる方法である。なお、メタルであるフェロニッケルは、還元処理を経て得られたメタルとスラグとを含む混合物から、そのメタルを分離することで回収することができる。
≪2. Nickel oxide ore smelting method >>
The nickel oxide ore smelting method according to the present embodiment is made by mixing and kneading nickel oxide ore, which is a smelting raw material, with a carbonaceous reducing agent or the like to form a mixture and subjecting the mixture to a reduction treatment. In this method, ferronickel, which is a metal, and slag are produced as reduction products. In addition, the ferronickel which is a metal can be collect | recovered by isolate | separating the metal from the mixture containing the metal and slag obtained through the reduction process.

 図1は、ニッケル酸化鉱石の製錬方法の流れの一例を示す工程図である。図1に示すように、このニッケル酸化鉱石の製錬方法は、ニッケル酸化鉱石と炭素質還元剤等の材料とを混合して混合物を得る混合処理工程S1と、得られた混合物を塊状化あるいは所定の容器に充填して成型する還元投入前処理工程S2と、所定の温度(還元温度)で混合物を還元する還元処理工程S3と、還元処理により生成したメタルとスラグとを含む混合物からメタルを分離して回収する分離工程S4と、を有する。 FIG. 1 is a process diagram showing an example of the flow of a nickel oxide ore smelting method. As shown in FIG. 1, this nickel oxide ore smelting method comprises mixing treatment step S1 in which nickel oxide ore and a material such as a carbonaceous reducing agent are mixed to obtain a mixture, and the resulting mixture is agglomerated or A reduction pre-treatment process S2 that fills and molds a predetermined container, a reduction process S3 that reduces the mixture at a predetermined temperature (reduction temperature), and a metal from a mixture that includes the metal and slag generated by the reduction process. Separating step S4 for separating and collecting.

 <2-1.混合処理工程>
 混合処理工程S1は、ニッケル酸化鉱石を含む原料粉末を混合して混合物を得る工程である。具体的に、混合処理工程S1では、製錬原料であるニッケル酸化鉱石と、鉄鉱石等の鉄源、フラックス成分、バインダー、炭素質還元剤等の、例えば粒径が0.1mm~0.8mm程度の原料粉末とを所定の割合で混合して混合物を得る。
<2-1. Mixing process>
The mixing treatment step S1 is a step of obtaining a mixture by mixing raw material powders containing nickel oxide ore. Specifically, in the mixing treatment step S1, nickel oxide ore which is a smelting raw material, iron source such as iron ore, flux component, binder, carbonaceous reducing agent, etc., for example, a particle size of 0.1 mm to 0.8 mm About a raw material powder is mixed at a predetermined ratio to obtain a mixture.

 製錬原料の鉱石であるニッケル酸化鉱石としては、特に限定されないが、リモナイト鉱、サプロライト鉱等を用いることができる。 The nickel oxide ore, which is a smelting raw material ore, is not particularly limited, and limonite or saprolite ore can be used.

 鉄源は、ニッケル酸化鉱石中のニッケルと反応してフェロニッケルを形成するために必要な鉄を供給するものである。鉄源としては、例えば鉄品位が50%程度以上の鉄鉱石、ニッケル酸化鉱石の湿式製錬により得られるヘマタイト等を用いることができる。 The iron source supplies iron necessary for reacting with nickel in nickel oxide ore to form ferronickel. As the iron source, for example, iron ore having an iron grade of about 50% or more, hematite obtained by wet smelting of nickel oxide ore, or the like can be used.

 下記表1に、原料であるニッケル酸化鉱石と、鉄鉱石の組成(重量%)の一例を示す。なお、原料の組成としては、これに限定されるものではない。 Table 1 below shows an example of the composition (wt%) of nickel oxide ore and iron ore as raw materials. In addition, as a composition of a raw material, it is not limited to this.

Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001

 また、バインダーとしては、例えば、ベントナイト、多糖類、樹脂、水ガラス、脱水ケーキ等を挙げることができる。また、フラックス成分としては、例えば、酸化カルシウム、水酸化カルシウム、炭酸カルシウム、二酸化珪素等を挙げることができる。 Examples of the binder include bentonite, polysaccharides, resins, water glass, and dehydrated cake. Examples of the flux component include calcium oxide, calcium hydroxide, calcium carbonate, silicon dioxide and the like.

 炭素質還元剤としては、特に限定されないが、例えば、石炭粉、コークス等が挙げられる。なお、この炭素質還元剤は、原料鉱石のニッケル酸化鉱石の粒度と同等の大きさを有するものであることが好ましい。また、炭素質還元剤の混合量としては、例えば、形成される混合物内に含まれる酸化ニッケルの全量をニッケルメタル還元するのに必要な化学当量と、ペレット内に含まれる酸化第二鉄を金属鉄に還元するのに必要な化学当量との両者合計値(便宜的に「化学当量の合計値」ともいう)を100%としたときに、好ましくは5質量%以上60質量%以下の炭素量の割合、より好ましくは10質量%以上40質量%以下の炭素量の割合となるように調整することができる。 Although it does not specifically limit as a carbonaceous reducing agent, For example, coal powder, coke, etc. are mentioned. In addition, it is preferable that this carbonaceous reducing agent has a magnitude | size equivalent to the particle size of the nickel oxide ore of a raw material ore. In addition, as the mixing amount of the carbonaceous reducing agent, for example, the chemical equivalent required to reduce the total amount of nickel oxide contained in the formed mixture to nickel metal and the ferric oxide contained in the pellets as metal When the total value of both chemical equivalents necessary for reduction to iron (also referred to as “total value of chemical equivalents” for convenience) is 100%, the carbon content is preferably 5% by mass to 60% by mass It is possible to adjust the ratio so as to be a ratio of carbon amount of 10% by mass to 40% by mass.

 炭素質還元剤の混合量として、化学当量の合計値100%に対して5質量%以上の炭素量となるようにすることで、ニッケルの還元性をより高め、生産性を高めることができる。一方で、60質量%以下の炭素量となるようにすることで、還元反応が進み過ぎることを抑制し、鉄の還元量の増加及びそれに伴うフェロニッケル中のニッケル品位の低下等を抑制し、得られるフェロニッケル合金中の品質をより高めることができる。このように、5質量%以上60質量%以下の炭素量の割合とすることで、ペレット等の形状にした原料表面に、金属成分により生成する殻(メタルシェル)を均一に生成させることができ、生産性、品質面でより好ましい。 The mixing amount of the carbonaceous reducing agent is such that the amount of carbon is 5% by mass or more with respect to 100% of the total value of chemical equivalents, whereby the reducibility of nickel can be further increased and the productivity can be increased. On the other hand, by reducing the amount of carbon to 60% by mass or less, it is possible to suppress the reduction reaction from proceeding excessively, to suppress an increase in the reduction amount of iron and the accompanying decrease in nickel quality in ferronickel, The quality in the obtained ferronickel alloy can be further improved. Thus, by setting the ratio of the carbon amount to 5% by mass or more and 60% by mass or less, a shell (metal shell) generated by a metal component can be uniformly generated on the surface of the raw material in the shape of pellets or the like. More preferable in terms of productivity and quality.

 なお、「ペレット」とは、少なくとも前記酸化鉱石と炭素質還元剤とを混合して得られる混合物を成形して得られる塊状のものをいい、単に「混合物」ともいう場合もある。 The “pellet” refers to a lump obtained by molding a mixture obtained by mixing at least the oxide ore and the carbonaceous reducing agent, and may be simply referred to as “mixture”.

 混合処理工程S1では、上述したようなニッケル酸化鉱石を含む原料粉末を均一に混合することによって混合物を得る。この混合に際しては、混練を同時に行ってもよく、混合後に混練を行ってもよい。このように、原料粉末を混合、混練することにより、原料同士の接触面積が増し、また空隙が減少することによって、還元反応が起りやすくなるとともに均一に反応させることができる。これにより、還元反応の反応時間を短縮させることができ、かつ品質のばらつきが無くなる。その結果として、生産性の高い処理することができ、かつ高い品質のフェロニッケルを製造することができる。 In the mixing treatment step S1, a mixture is obtained by uniformly mixing the raw material powder containing the nickel oxide ore as described above. In this mixing, kneading may be performed simultaneously, or kneading may be performed after mixing. Thus, by mixing and kneading the raw material powder, the contact area between the raw materials is increased and the voids are reduced, so that a reduction reaction is easily caused and a uniform reaction can be achieved. Thereby, the reaction time of the reduction reaction can be shortened, and quality variation is eliminated. As a result, it is possible to process with high productivity and to manufacture high quality ferronickel.

 また、原料粉末を混練した後、押出機を用いて押出してもよい。このように押出機で押出すことによって、より一層高い混練効果を得ることができ、原料粉末同士の接触面積が増し、また空隙が減少させることができる。これにより、高品質のフェロニッケルを効率的に製造することができる。 Further, after the raw material powder is kneaded, it may be extruded using an extruder. Thus, by extruding with an extruder, a much higher kneading effect can be obtained, the contact area between the raw material powders can be increased, and the voids can be reduced. Thereby, high quality ferronickel can be produced efficiently.

 <2-2.還元投入前処理工程(前処理工程)>
 還元投入前処理工程S2は、混合処理工程S1で得られた混合物を、塊状化して塊状物とし、あるいは容器に充填して成型する工程である。すなわち、この還元投入前処理工程S2では、原料粉末を混合して得られた混合物を、後述する還元処理工程S3にて使用する炉に投入し易くし、また効率的に還元反応が起こるように成形する。
<2-2. Reduction input pretreatment process (pretreatment process)>
The pre-reduction process step S2 is a step in which the mixture obtained in the mixing step S1 is agglomerated into a mass or filled into a container and molded. That is, in this pre-reduction charging treatment step S2, the mixture obtained by mixing the raw material powders can be easily put into a furnace used in the reduction treatment step S3 described later, and the reduction reaction can be efficiently performed. Mold.

 (混合物の塊状化)
 得られた混合物を塊状化する場合には、その混合物を塊状物に成型(造粒)する。具体的には、得られた混合物に対して塊状化に必要な所定量の水分を添加し、例えば塊状物製造装置(転動造粒機、圧縮成形機、押出成形機等、「ペレタイザー」ともいう)等を用いて塊状(以下、「ペレット」ともいう)に成型する。
(Agglomeration of the mixture)
When the obtained mixture is agglomerated, the mixture is molded (granulated) into a lump. Specifically, a predetermined amount of moisture necessary for agglomeration is added to the obtained mixture, and for example, an agglomerate production apparatus (such as a tumbling granulator, a compression molding machine, an extrusion molding machine, etc.) And the like (hereinafter also referred to as “pellets”).

 ペレットの形状としては、特に限定されず、球状、立方体形状、直方体形状等とすることができる。例えば、球状のペレットであることにより、還元反応が比較的均一に進み易く好ましい。また、立方体形状、直方体形状のペレットであることにより、炉床に敷かれた床敷材上に安定的に載置させることができ、ハンドリング性が向上する。 The shape of the pellet is not particularly limited, and may be a spherical shape, a cubic shape, a rectangular parallelepiped shape, or the like. For example, a spherical pellet is preferable because the reduction reaction easily proceeds relatively uniformly. Moreover, since it is a cube shape and a rectangular parallelepiped pellet, it can be stably mounted on the floor covering material laid on the hearth, and handling property improves.

 また、ペレット状にする塊状物の大きさとしては、特に限定されないが、例えば、乾燥処理(乾燥工程S31)、予熱処理(予熱工程S32)を経て、還元処理(還元工程S33)を行うために使用する製錬炉等に装入されるペレットの大きさ(球状のペレットの場合には直径)で、10mm~30mm程度となるようにすることができる。なお、還元工程等については、詳しくは後述する。 In addition, the size of the lump to be pelletized is not particularly limited. For example, in order to perform the reduction process (reduction process S33) through the drying process (drying process S31) and the preheating process (preheating process S32). The size of the pellets charged into the smelting furnace to be used (diameter in the case of spherical pellets) can be about 10 mm to 30 mm. Details of the reduction step will be described later.

 (混合物の容器への充填)
 得られた混合物を容器に充填して成型する場合には、その混合物を押出機等で混練しながら所定の容器に充填することができる。容器に充填した混合物をプレス等により押し固めることが好ましい。容器内で混合物を押し固めて成形し、容器から取り出して次工程の還元処理工程S3に付すことによって、混合物の密度を上げることができるとともに、密度が均一化し、還元反応がより均一に進み易くなり、品質ばらつきの小さいフェロニッケルを製造することができる。
(Filling the mixture into the container)
When the obtained mixture is filled into a container and molded, the mixture can be filled into a predetermined container while kneading with an extruder or the like. The mixture filled in the container is preferably pressed and hardened. By pressing and solidifying the mixture in the container, taking out from the container and subjecting it to the subsequent reduction treatment step S3, the density of the mixture can be increased, the density becomes uniform, and the reduction reaction proceeds more uniformly. Thus, ferronickel with small quality variation can be manufactured.

 容器内に充填する混合物の形状としては、特に限定されないが、例えば球状、直方体状、立方体状、円柱状等とすることが好ましい。また、その大きさについても特に限定されないが、例えば球状であれば、概ね直径が500mm以下であることが好ましい。また、例えば直方体形状や立方体形状であれば、概ね、縦、横の内寸が500mm以下であることが好ましい。このような形状、大きさとすることにより、品質ばらつきが小さく、かつ生産性の高い製錬を行うことができる。 The shape of the mixture filled in the container is not particularly limited, but is preferably, for example, spherical, rectangular parallelepiped, cubic or cylindrical. Moreover, although the size is not particularly limited, for example, if it is spherical, it is preferable that the diameter is approximately 500 mm or less. For example, in the case of a rectangular parallelepiped shape or a cubic shape, it is generally preferable that the vertical and horizontal inner dimensions are 500 mm or less. By adopting such a shape and size, smelting with small quality variation and high productivity can be performed.

 <2-3.還元処理工程>
 還元処理工程S3では、例えば、混合処理工程S1にて原料粉末が混合され、還元投入前処理工程S2にて塊状化された混合物、あるいは容器に充填され成型された混合物を、還元炉内で所定の還元温度にて還元加熱する。そして、還元処理工程S3における混合物の還元加熱処理により、製錬反応が進行して、メタルとスラグとが生成する。
<2-3. Reduction process>
In the reduction treatment step S3, for example, the raw material powder is mixed in the mixing treatment step S1 and the mixture agglomerated in the reduction charging pretreatment step S2 or the mixture filled in the container and molded is predetermined in the reduction furnace. Reduce and heat at the reduction temperature of And a smelting reaction advances by the reduction | restoration heat processing of the mixture in reduction process process S3, and a metal and slag produce | generate.

 ここで、この加熱還元に際し、床敷材として、アルミナ、アルミナセメント、マグネシア、マグネシアセメント、ジルコニア、ジルコニアセメント及びムライトから選ばれる1種以上の材料から構成されるものを用いる。このような床敷材を還元炉の炉床に敷き、その床敷材上に混合物を載置させて加熱還元することにより、混合物と還元炉の炉床との直接の反応を抑制することができる。また、上述したような種類の床敷材を用いることで、混合物との反応を抑制することができ、高品質のフェロニッケルを製造できる。なお、混合物との反応が抑制されることから、その床敷材を再利用することができ、製錬コストを低下させることができる。 Here, at the time of this heat reduction, as the flooring material, a material composed of one or more materials selected from alumina, alumina cement, magnesia, magnesia cement, zirconia, zirconia cement and mullite is used. By placing such a flooring material on the hearth of the reduction furnace and placing the mixture on the flooring material and reducing the heat, the direct reaction between the mixture and the hearth of the reduction furnace can be suppressed. it can. Moreover, reaction with a mixture can be suppressed by using the kind of floor covering material as described above, and high-quality ferronickel can be produced. In addition, since reaction with a mixture is suppressed, the flooring material can be reused and smelting cost can be reduced.

 図2は、還元処理工程S3にて実行する処理工程を示す工程図である。図2に示すように、還元処理工程S3は、混合物を乾燥する乾燥工程S31と、乾燥させた混合物を予熱する予熱工程S32と、混合物を還元する還元工程S33と、得られた還元物を冷却する冷却工程S35と、を有する。また、還元工程S33を経て得られた還元物を所定の温度範囲に保持する温度保持工程S34を有する。 FIG. 2 is a process diagram showing the process executed in the reduction process S3. As shown in FIG. 2, the reduction treatment step S3 includes a drying step S31 for drying the mixture, a preheating step S32 for preheating the dried mixture, a reduction step S33 for reducing the mixture, and cooling the obtained reduction product. Cooling step S35. Moreover, it has the temperature holding process S34 which hold | maintains the reduced material obtained through reduction process S33 in a predetermined temperature range.

 ここで、還元工程S33における処理は、還元炉を用いて行われる。還元炉としては、例えば移動式炉床炉又は回転炉床炉を用いることができる。また、還元物を所定の温度範囲に保持する温度保持工程S34を実行する場合には、少なくとも、還元工程S33における処理と温度保持工程S34における処理とを一つの還元炉内にて実行する。 Here, the process in the reduction step S33 is performed using a reduction furnace. As the reduction furnace, for example, a mobile hearth furnace or a rotary hearth furnace can be used. Moreover, when performing temperature holding process S34 which hold | maintains a reduced product in a predetermined | prescribed temperature range, at least the process in reduction process S33 and the process in temperature holding process S34 are performed within one reducing furnace.

 このように、これらの処理を一つの還元炉内にて行うことによって、その還元炉内の温度を高い温度で維持することができるため、それぞれの工程における処理の都度、温度を上げたり下げたりする等の必要が無くなり、エネルギーコストを低減することができる。このことから、高い生産性でもって品質の良好なフェロニッケルを連続して安定的に製造することができる。 In this way, by performing these treatments in one reducing furnace, the temperature in the reducing furnace can be maintained at a high temperature, so that the temperature can be raised or lowered at each treatment in each process. There is no need to do so and the energy cost can be reduced. From this, it is possible to continuously and stably manufacture ferronickel with good quality with high productivity.

 (1)乾燥工程
 乾燥工程S31では、原料粉末を混合して得られた混合物に対して乾燥処理を施す。この乾燥工程S31は、主に混合物中の水分や結晶水を飛ばすことを目的とする。
(1) Drying process In drying process S31, a drying process is performed with respect to the mixture obtained by mixing raw material powder. The purpose of this drying step S31 is mainly to remove water and crystal water in the mixture.

 混合処理工程S1にて得られた混合物には水分等が多く含まれており、そのような状態で還元処理時に還元温度のような高温まで急加熱すると水分が一気に気化、膨張し、塊状化した混合物が割れ、場合によって破裂して粉々になってしまい、均一な還元処理を行うことが困難になる。そのため、還元処理を行うに先立ち、混合物に対する乾燥処理を施して水分を除去するようにし、ペレット等の破壊を防止する。 The mixture obtained in the mixing treatment step S1 contains a lot of moisture and the like, and when rapidly heated to a high temperature such as the reduction temperature during the reduction treatment, the moisture is vaporized, expanded and agglomerated at once. The mixture cracks, and in some cases, ruptures into pieces, making it difficult to perform uniform reduction treatment. Therefore, prior to the reduction treatment, the mixture is subjected to a drying treatment to remove moisture, thereby preventing the destruction of pellets and the like.

 乾燥工程S31における乾燥処理は、還元炉に接続される形態で行われることが好ましい。還元炉内において乾燥処理を施すエリア(乾燥エリア)を設けて実施することも考えられるが、このような場合、乾燥エリアでの乾燥処理が律速となって、還元工程S33における処理や温度保持工程S34における処理に影響を与える可能性がある。 It is preferable that the drying process in drying process S31 is performed in the form connected to a reduction furnace. Although it can be considered to provide an area (drying area) for performing a drying process in the reduction furnace, in such a case, the drying process in the drying area becomes rate-limiting, and the process in the reduction process S33 and the temperature holding process are performed. There is a possibility of affecting the processing in S34.

 したがって、乾燥工程S31における乾燥処理は、還元炉の炉外に設けられ、その還元炉に接続された乾燥室にて行われることが好ましい。なお、詳しくは後述するが、図3に、還元炉の一例である回転炉床炉1と、その回転炉床炉1に接続された乾燥室20の構成例を示す。このように、回転炉床炉1の炉外に乾燥室20を設けることで、後述する予熱、還元、冷却といった工程とは全く別に乾燥室を設計でき、望ましい乾燥処理、予熱処理、還元処理、冷却処理をそれぞれ実行し易くなる。例えば、原料に依存して混合物に水分が多く残存するような場合には、乾燥処理に時間がかかるため、乾燥室20の全長を長めに設計すればよく、または乾燥室20内での混合物の搬送速度が遅くなるように設計すればよい。 Therefore, it is preferable that the drying process in the drying step S31 is performed in a drying chamber provided outside the reduction furnace and connected to the reduction furnace. Although described in detail later, FIG. 3 shows a configuration example of a rotary hearth furnace 1 which is an example of a reduction furnace and a drying chamber 20 connected to the rotary hearth furnace 1. Thus, by providing the drying chamber 20 outside the rotary hearth furnace 1, the drying chamber can be designed completely different from the steps such as preheating, reduction, and cooling described later, and desirable drying treatment, preheat treatment, reduction treatment, It becomes easy to perform each cooling process. For example, when a lot of moisture remains in the mixture depending on the raw material, the drying process takes time. Therefore, the drying chamber 20 may be designed to have a long overall length, or the mixture in the drying chamber 20 What is necessary is just to design so that a conveyance speed may become slow.

 乾燥室20における乾燥処理としては、例えば、混合物中の固形分が70重量%程度で、水分が30重量%程度となるように処理することができる。また、乾燥方法については、特に限定されないが、乾燥室20において搬送されてきた混合物に対し熱風を吹き付けることによって行うことができる。また、乾燥温度についても、特に限定されないが、還元反応がはじまらないようにする観点から、500℃以下とすることが好ましく、かつその500℃以下の温度で均一に乾燥することが好ましい。 As the drying treatment in the drying chamber 20, for example, the solid content in the mixture can be about 70% by weight and the water content can be about 30% by weight. Further, the drying method is not particularly limited, but can be performed by blowing hot air on the mixture conveyed in the drying chamber 20. Also, the drying temperature is not particularly limited, but from the viewpoint of preventing the reduction reaction from starting, it is preferably 500 ° C. or lower, and it is preferable to uniformly dry at the temperature of 500 ° C. or lower.

 下記表2に、乾燥処理後の混合物における固形分の組成(重量部)の一例を示す。なお、混合物の組成としては、これに限定されるものではない。 Table 2 below shows an example of the composition (parts by weight) of the solid content in the mixture after the drying treatment. The composition of the mixture is not limited to this.

Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002

 (2)予熱工程
 予熱工程S32では、乾燥工程S31での乾燥処理により水分を除去した後の混合物を予熱(予備加熱)する。
(2) Preheating process In preheating process S32, the mixture after water | moisture content was removed by the drying process in drying process S31 is preheated (preheating).

 混合物を還元炉に装入していきなり高温の還元温度まで昇温すると、熱応力によって混合物が割れたり、粉状になってしまったりすることがある。また、混合物の温度が均一に上がらず、還元反応にばらつきが生じ、生成されるメタルの品質がばらつくことがある。そのため、混合物に対して乾燥処理を施した後に、所定の温度にまで予熱することが好ましく、これにより混合物の破壊や還元反応のばらつきを抑えることができる。 When the mixture is charged into a reduction furnace and heated to a high reduction temperature, the mixture may break or become powdery due to thermal stress. In addition, the temperature of the mixture may not rise uniformly, causing variations in the reduction reaction, and the quality of the metal produced may vary. For this reason, it is preferable to preheat the mixture to a predetermined temperature after the drying treatment, whereby the destruction of the mixture and variations in the reduction reaction can be suppressed.

 予熱工程S32における予熱処理は、乾燥処理と同様に、還元炉の炉外に設けられた処理室にて行われることが好ましく、その還元炉に接続された予熱室にて行われるようにすることが好ましい。なお、図3に、還元炉の一例である回転炉床炉1に接続された予熱室30の構成例を示すが、この予熱室30は回転炉床炉1の炉外に設けられており、乾燥処理を行う乾燥室20から連続的に設けられている。このように、回転炉床炉1の炉外に設けられた予熱室30にて予熱処理を行うことによって、還元処理を実行する回転炉床炉1内の温度を高い温度で維持でき、回転炉床炉1内の再加熱に必要なエネルギーを大幅に削減することができる。 The preheating process in the preheating step S32 is preferably performed in a processing chamber provided outside the reduction furnace, similarly to the drying process, and is performed in a preheating chamber connected to the reduction furnace. Is preferred. FIG. 3 shows a configuration example of the preheating chamber 30 connected to the rotary hearth furnace 1 which is an example of the reduction furnace. The preheating chamber 30 is provided outside the rotary hearth furnace 1. It is continuously provided from the drying chamber 20 that performs the drying process. Thus, by performing the pre-heat treatment in the pre-heating chamber 30 provided outside the rotary hearth furnace 1, the temperature in the rotary hearth furnace 1 for performing the reduction process can be maintained at a high temperature, and the rotary furnace The energy required for reheating in the floor furnace 1 can be greatly reduced.

 予熱室30における予熱処理としては、特に限定されないが、予熱温度を600℃以上として行うことが好ましく、予熱温度を700℃以上1280℃以下として行うことがより好ましい。このような範囲の予熱温度で処理することによって、続く還元処理における還元温度まで再加熱する際に必要なエネルギーを大幅に削減することができる。 The preheat treatment in the preheating chamber 30 is not particularly limited, but is preferably performed at a preheating temperature of 600 ° C or higher, and more preferably at a preheating temperature of 700 ° C or higher and 1280 ° C or lower. By processing at the preheating temperature in such a range, the energy required for reheating to the reduction temperature in the subsequent reduction process can be greatly reduced.

 (3)還元工程
 還元工程S33では、予熱工程S32にて予熱した混合物を所定の還元温度で還元処理する。還元工程S33における還元処理は、例えば移動式炉床炉又は回転炉床炉等の還元炉を用いて行うことができる。そして、この還元炉の炉床には、床敷材を配置し、その床敷材の上にニッケル酸化鉱石と炭素質還元剤との混合物を載置する。上述したとおり、還元の具体的態様としては、4つの態様が存在する。以下、それぞれの態様について説明する。
(3) Reduction step In the reduction step S33, the mixture preheated in the preheating step S32 is reduced at a predetermined reduction temperature. The reduction process in the reduction step S33 can be performed using a reduction furnace such as a mobile hearth furnace or a rotary hearth furnace. And a floor covering material is arrange | positioned on the hearth of this reduction furnace, and the mixture of a nickel oxide ore and a carbonaceous reducing agent is mounted on the floor covering material. As described above, there are four specific modes of reduction. Each aspect will be described below.

 (3-1)第1の態様の還元工程
 第1の態様の還元工程では、床敷材としてアルミナ、アルミナセメント、マグネシア、マグネシアセメント、ジルコニア、ジルコニアセメント及びムライトから選択される1種以上の材料から構成されるものを配置し、その床敷材の上にニッケル酸化鉱石と炭素質還元剤との混合物を還元炉の炉床に載置してニッケル酸化鉱石の還元を行う。
(3-1) Reduction Process of First Aspect In the reduction process of the first aspect, at least one material selected from alumina, alumina cement, magnesia, magnesia cement, zirconia, zirconia cement and mullite as a flooring material. The mixture of nickel oxide ore and carbonaceous reducing agent is placed on the floor covering material and placed on the hearth of the reduction furnace to reduce the nickel oxide ore.

 このようにして、特定の床敷材を還元炉の炉床に配置し、その床敷材上に混合物を載置して還元処理を施すことにより、混合物と炉床との反応や、混合物と床敷材との反応を抑制することができ、高品質のフェロニッケルを製造することができる。また、得られた還元物を有効に回収することができる。さらに、床敷材を再利用することにより、製錬のコストを低下させることができる。 In this way, by placing a specific flooring material on the hearth of the reduction furnace, placing the mixture on the flooring material and performing a reduction treatment, the reaction between the mixture and the hearth, the mixture and Reaction with the flooring material can be suppressed, and high-quality ferronickel can be produced. Moreover, the obtained reduced product can be recovered effectively. Furthermore, the cost of smelting can be reduced by reusing the flooring material.

 床敷材の形状としては、特に限定されないが、例えば粒子(床敷材粒子)から構成されるものを用いることが好ましい。床敷材粒子により床敷材を構成することで、混合物と床敷材との接触面積が適当なものとなり、また、炉床に敷き詰める際の操作性や、炉床から回収する際の取り扱い性にも優れる。なお、混合物と床敷材との接触面積が大きすぎると、混合物と床敷材との反応が進行するおそれがある。一方で、接触面積が小さすぎると、生成したスラグやメタルが床敷材の隙間に染み込むおそれがある。 The shape of the flooring material is not particularly limited, but for example, it is preferable to use a material composed of particles (flooring material particles). By configuring the flooring material with the flooring material particles, the contact area between the mixture and the flooring material becomes appropriate, and the operability when spreading on the hearth and the handling when recovering from the hearth Also excellent. In addition, when the contact area of a mixture and a flooring material is too large, there exists a possibility that reaction with a mixture and a flooring material may advance. On the other hand, if the contact area is too small, the generated slag or metal may penetrate into the gap between the flooring materials.

 床敷材として、粒子から構成されるものを用いる場合、平均床敷材体積率が、例えば3%以上のものであることが好ましく、4%以上のものであることがより好ましく、5%以上のものであることがさらに好ましい。一方で、平均床敷材体積率は、85%以下のものであることが好ましく、82%以下のものであることがより好ましく、80%以下のものであることがさらに好ましい。平均床敷材体積率がこのような範囲の床敷材を用いることにより、混合物と床敷材との接触面積がより適当なものとなる。 When using a material composed of particles as the flooring material, the average flooring material volume ratio is, for example, preferably 3% or more, more preferably 4% or more, and more preferably 5% or more. More preferably. On the other hand, the average floor covering volume ratio is preferably 85% or less, more preferably 82% or less, and further preferably 80% or less. By using a flooring material having an average flooring material volume ratio in such a range, the contact area between the mixture and the flooring material becomes more appropriate.

 ここで、第1の態様において「平均床敷材体積率」とは、任意の300個の床敷材粒子の体積率(床敷材体積率)の平均値であり、下記式(1)により求められる。また、「床敷材体積率」とは、床敷材粒子の最大粒子長を直径とする球の体積を100%としたときの、その床敷材体積の割合であり、下記式(2)により求められる。
 平均床敷材体積率
 =床敷材粒子300個の床敷材体積率の総和/300  ・・・(1)
 床敷材体積率
 =(床敷材粒子の体積/床敷材粒子の最大粒子長を直径とする球の体積)×100  ・・・(2)
Here, in the first aspect, the “average flooring material volume ratio” is an average value of the volume ratios (flooring material volume ratios) of arbitrary 300 flooring material particles, according to the following formula (1). Desired. Further, the “floor volume ratio” is the ratio of the volume of the flooring material when the volume of the sphere having the maximum particle length of the flooring material particle is 100%, and the following formula (2) It is calculated by.
Average floor covering volume ratio = total floor covering volume ratio of 300 floor covering particles / 300 (1)
Floor covering volume ratio = (volume of floor covering particles / volume of sphere having diameter of maximum particle length of floor covering particles) × 100 (2)

 第1の態様において、上記式(2)の「最大粒子長」とは、ある特定の粒子において、最も長い直径や辺をいう。具体的には、粒子が楕円状であれば最大粒子長は長径であり、直方体であれば最大粒子長は対角線をいう。したがって、第1の態様において「床敷材粒子の最大粒子長を直径とする球」とは、床敷材粒子に接し、且つ床敷材粒子を内包する球のことをいう。 In the first embodiment, the “maximum particle length” in the above formula (2) refers to the longest diameter or side of a specific particle. Specifically, if the particles are elliptical, the maximum particle length is the major axis, and if the particles are rectangular parallelepiped, the maximum particle length is a diagonal line. Therefore, in the first embodiment, “a sphere having a diameter of the maximum particle length of the flooring material particles” refers to a sphere that is in contact with the flooring material particles and encloses the flooring material particles.

 図4は、不定形粒子及びその最大粒子長を直径とする球の模式図である。不定形粒子である場合には、図4のようにして最大粒子長を決定する。なお、第1の態様においてこの「最大粒子長」は、金属顕微鏡を用いて測定することができる。一方で、床敷材粒子の体積は、床敷材の密度が既知であることから、重量を測定することにより算出することができる。このようにして、無作為に選択した床敷材粒子300個を測定し、床敷材体積率を求め、式(1)により、平均床敷材体積率を算出する。 FIG. 4 is a schematic diagram of an irregularly shaped particle and a sphere whose diameter is the maximum particle length. In the case of irregular particles, the maximum particle length is determined as shown in FIG. In the first embodiment, the “maximum particle length” can be measured using a metal microscope. On the other hand, the volume of the flooring material particles can be calculated by measuring the weight because the density of the flooring material is known. In this way, 300 randomly selected flooring material particles are measured, the flooring material volume ratio is obtained, and the average flooring material volume ratio is calculated by Equation (1).

 床敷材として、粒子から構成されるものを用いる場合、床敷材粒子の大きさとしては、特に限定されないが、平均最大粒子長が10μm以上であることが好ましく、15μm以上であることがより好ましく、20μm以上であることがより好ましい。一方で、平均最大粒子長は、6000μm以下であることが好ましく、5500μm以下であることがより好ましく、5000μm以下であることがさらに好ましい。平均最大粒子長がこのような範囲の床敷材であることにより、床敷材上に載置する混合物とその床敷材との接触面積が適当なものとなる。 When using a material composed of particles as the flooring material, the size of the flooring material particles is not particularly limited, but the average maximum particle length is preferably 10 μm or more, more preferably 15 μm or more. Preferably, it is 20 μm or more. On the other hand, the average maximum particle length is preferably 6000 μm or less, more preferably 5500 μm or less, and even more preferably 5000 μm or less. When the average maximum particle length is a flooring material in such a range, the contact area between the mixture placed on the flooring material and the flooring material becomes appropriate.

 ここで、第1の態様において「平均最大粒子長」とは、無作為に選択した床敷材粒子300個の平均の最大粒子長をいい、下記式(3)により求められる。
 平均最大粒子長=床敷材300個の最大粒子長の総和/300 ・・・(3)
Here, in the first embodiment, the “average maximum particle length” refers to the average maximum particle length of 300 randomly selected floor covering particles, and is obtained by the following formula (3).
Average maximum particle length = the sum of the maximum particle lengths of 300 flooring materials / 300 (3)

 床敷材として、粒子から構成されるものを用いる場合、床敷材粒子の比表面積としては、特に限定されないが、例えば、0.001μm-1以上であることが好ましく、0.002μm-1以上であることがより好ましく、0.003μm-1以上であることがさらに好ましい。一方で、比表面積としては、例えば、3.0μm-1以下であることが好ましく、2.5μm-1以下であることがより好ましく、2.0μm-1以下であることがさらに好ましい。比表面積がこのような範囲の床敷材を用いることにより、混合物と床敷材の接触面積がより適当なものとなる。なお、「比表面積」は、一般的な比表面積測定装置を用いて測定することができる。 As bedding material, if used those composed of particles, the specific surface area of the bedding material particles is not particularly limited, for example, is preferably 0.001 [mu] m -1 or more, 0.002 .mu.m -1 or More preferably, it is 0.003 μm −1 or more. On the other hand, as the specific surface area, for example, is preferably 3.0 [mu] m -1 or less, more preferably 2.5 [mu] m -1 or less, more preferably 2.0 .mu.m -1 or less. By using a flooring material having a specific surface area in such a range, the contact area between the mixture and the flooring material becomes more appropriate. The “specific surface area” can be measured using a general specific surface area measuring apparatus.

 混合物の炉床に対する配置率としては、特に限定されないが、例えば、炉床を平面視したときにその炉床の面積の1%以上となるように混合物を配置することが好ましく、1.5%以上となるように混合物を配置することがより好ましく、2%以上となるように混合物を配置することがさらに好ましい。一方で、混合物の炉床に対する配置率としては、炉床の面積の50%以下となるように混合物が配置することが好ましく、45%以下となるように混合物を配置することがより好ましく、42%以下となるように混合物を配置することがさらに好ましく、40%以下となるように混合物を配置することが特に好ましい。 The placement ratio of the mixture with respect to the hearth is not particularly limited. For example, it is preferable to arrange the mixture so that it becomes 1% or more of the area of the hearth when viewed in plan, It is more preferable to arrange the mixture so as to achieve the above, and it is even more preferable to arrange the mixture so as to be 2% or more. On the other hand, as an arrangement ratio of the mixture with respect to the hearth, the mixture is preferably arranged so as to be 50% or less of the area of the hearth, and more preferably, the mixture is arranged so as to be 45% or less. It is more preferable to arrange the mixture so as to be not more than%, and it is particularly preferable to arrange the mixture so as to be not more than 40%.

 (3-2)第2の態様の還元工程
 第2の態様の還元工程では、比表面積が0.001μm-1以上3.0μm-1以下であり、且つ平均最大粒子長が15.0μm以上2000μm以下である床敷材(床敷材粒子)を還元炉の炉床に配置し、その床敷材の上にニッケル酸化鉱石と炭素質還元剤との混合物を載置してニッケル酸化鉱石の還元を行う。
(3-2) In the reduction step of the reduction step a second embodiment of the second aspect, the specific surface area is at 0.001 [mu] m -1 or more 3.0 [mu] m -1 or less, and an average maximum particle length of more than 15.0 .mu.m 2000 .mu.m The following flooring material (flooring material particles) is placed in the hearth of the reduction furnace, and a mixture of nickel oxide ore and carbonaceous reducing agent is placed on the flooring material to reduce the nickel oxide ore. I do.

 このようにして、特定の床敷材粒子を還元炉の炉床に配置し、その床敷材上に混合物を載置して還元処理を施すことにより、混合物と炉床との反応及び混合物と床敷材との反応を抑制することができ、高品質のフェロニッケルを製造することができ、また有効に回収することができる。また、床敷材を再利用することにより、製錬のコストを低下させることができる。 In this way, specific flooring particles are placed on the hearth of the reduction furnace, and the mixture is placed on the flooring material and subjected to reduction treatment, whereby the reaction between the mixture and the hearth and the mixture Reaction with the flooring material can be suppressed, high quality ferronickel can be produced, and can be effectively recovered. Moreover, the cost of smelting can be reduced by reusing the flooring material.

 ここで、床敷材としては、粒子から構成されるものを用いる。そして、この床敷材粒子は、比表面積が0.001μm-1以上3.0μm-1以下であり、且つ平均最大粒子長が15.0μm以上2000μm以下である。粒子から構成され、且つ比表面積及び平均最大粒子長がこのような範囲にある床敷材を用いることにより、混合物と床敷材との接触面積が適当なものとなる。なお、混合物と床敷材との接触面積が大きすぎると、両者の反応が進行するおそれがある。一方で、接触面積が小さすぎると、生成したスラグやメタルが床敷材の隙間に染み込むおそれがある。なお、「比表面積」は、一般的な比表面積測定装置を用いて測定することができる。 Here, what is comprised from particle | grains is used as a floor covering material. The flooring particles have a specific surface area of 0.001 μm −1 to 3.0 μm −1 and an average maximum particle length of 15.0 μm to 2000 μm. By using a flooring material composed of particles and having a specific surface area and an average maximum particle length in such ranges, the contact area between the mixture and the flooring material becomes appropriate. In addition, when the contact area of a mixture and a flooring material is too large, there exists a possibility that reaction of both may advance. On the other hand, if the contact area is too small, the generated slag or metal may penetrate into the gap between the flooring materials. The “specific surface area” can be measured using a general specific surface area measuring apparatus.

 また、第2の態様において「最大粒子長」とは、ある特定の粒子において、最も長い直径や辺をいう。具体的には、粒子が楕円状であれば最大粒子長は長径であり、直方体であれば最大粒子長は対角線をいう。図5は、不定形粒子の最大粒子長を示す模式図である。不定形粒子である場合には、図5のように最大粒子長を決定する。この「最大粒子長」は、金属顕微鏡を用いて測定することができる。そして、第2の態様において「平均最大粒子長」は、無作為に選定した床敷材粒子300個の最大粒子長の平均値である。 In the second embodiment, “maximum particle length” refers to the longest diameter or side of a specific particle. Specifically, if the particles are elliptical, the maximum particle length is the major axis, and if the particles are rectangular parallelepiped, the maximum particle length is a diagonal line. FIG. 5 is a schematic diagram showing the maximum particle length of irregular shaped particles. In the case of irregularly shaped particles, the maximum particle length is determined as shown in FIG. This “maximum particle length” can be measured using a metallographic microscope. In the second embodiment, the “average maximum particle length” is an average value of the maximum particle lengths of 300 randomly selected floor covering particles.

 床敷材粒子としては、特に限定されないが、アルミナ、アルミナセメント、マグネシア、マグネシアセメント、ジルコニア、ジルコニアセメント及びムライトから選択される1種以上の材料から構成されるもの用いることが好ましい。このような床敷材を用いることにより、混合物と炉床との反応及び混合物と床敷材との反応をさらに抑制することができ、高品質のフェロニッケルを製造することができ、また有効に回収することができる。また、床敷材を再利用することにより、製錬のコストを低下させることができる。 The bedding material particles are not particularly limited, but it is preferable to use those composed of one or more materials selected from alumina, alumina cement, magnesia, magnesia cement, zirconia, zirconia cement and mullite. By using such a flooring material, the reaction between the mixture and the hearth and the reaction between the mixture and the flooring material can be further suppressed, and high-quality ferronickel can be produced and effectively used. It can be recovered. Moreover, the cost of smelting can be reduced by reusing the flooring material.

 また、床敷材粒子の比表面積は、0.002μm-1以上であることが好ましく、0.003μm-1以上であることがより好ましい。一方で、比表面積は、2.5μm-1以下であることが好ましく、2.0μm-1以下であることがより好ましい。床敷材粒子の比表面積がこのような範囲の床敷材を用いることにより、床敷材上に載置する混合物とその床敷材との接触面積がより適当なものとなる。 The specific surface area of the bedding material particles is preferably 0.002 .mu.m -1 or more, and more preferably 0.003 .mu.m -1 or more. On the other hand, the specific surface area is preferably 2.5 [mu] m -1 or less, more preferably 2.0 .mu.m -1 or less. By using a flooring material in which the specific surface area of the flooring material particles is in such a range, the contact area between the mixture placed on the flooring material and the flooring material becomes more appropriate.

 床敷材粒子の平均最大粒子長は、17.0μm以上であることが好ましく、20.0μm以上であることがより好ましい。一方で、床敷材粒子の平均最大粒子長は、1500μm以下のものであることが好ましく、1200μm以下であることがより好ましく、1000μm以下であることがさらに好ましい。床敷材粒子の平均最大粒子長がこのような範囲の床敷材を用いることにより、床敷材上に載置する混合物とその床敷材との接触面積がより適当なものとなる。 The average maximum particle length of the flooring particles is preferably 17.0 μm or more, and more preferably 20.0 μm or more. On the other hand, the average maximum particle length of the flooring particles is preferably 1500 μm or less, more preferably 1200 μm or less, and even more preferably 1000 μm or less. By using a flooring material having an average maximum particle length of the flooring material particles in such a range, the contact area between the mixture placed on the flooring material and the flooring material becomes more appropriate.

 混合物の炉床に対する配置率としては、特に限定されないが、例えば、炉床を平面視したときにその炉床の面積の1%以上となるように混合物を配置することが好ましく、1.5%以上となるように混合物を配置することがより好ましく、2%以上となるように混合物を配置することがさらに好ましい。一方で、混合物の炉床に対する配置率としては、炉床の面積の50%以下となるように混合物が配置することが好ましく、45%以下となるように混合物を配置することがより好ましく、42%以下となるように混合物を配置することがさらに好ましく、40%以下となるように混合物を配置することが特に好ましい。 The placement ratio of the mixture with respect to the hearth is not particularly limited. For example, it is preferable to arrange the mixture so that it becomes 1% or more of the area of the hearth when viewed in plan, It is more preferable to arrange the mixture so as to achieve the above, and it is even more preferable to arrange the mixture so as to be 2% or more. On the other hand, as an arrangement ratio of the mixture with respect to the hearth, the mixture is preferably arranged so as to be 50% or less of the area of the hearth, and more preferably, the mixture is arranged so as to be 45% or less. It is more preferable to arrange the mixture so as to be not more than%, and it is particularly preferable to arrange the mixture so as to be not more than 40%.

 (3-3)第3の態様の還元工程
 第3の態様では、床敷材として、粒子(床敷材粒子)から構成され、その床敷材に含まれる最大粒子長が50.0μm以下の床敷材粒子の数が、床敷材に含まれる総床敷材粒子の数に対し1%以上40%以下であり、その平均最大粒子長が40.0μm以上1050μm以下であるものを還元炉の炉床に配置し、その床敷材の上にニッケル酸化鉱石と炭素質還元剤との混合物を載置して、ニッケル酸化鉱石の還元を行う。
(3-3) Reduction Step of Third Aspect In the third aspect, the floor covering material is composed of particles (floor covering material particles), and the maximum particle length contained in the floor covering material is 50.0 μm or less. A reduction furnace in which the number of flooring particles is 1% or more and 40% or less with respect to the total number of flooring particles contained in the flooring material, and the average maximum particle length is 40.0 μm or more and 1050 μm or less The mixture of nickel oxide ore and carbonaceous reductant is placed on the floor covering material to reduce the nickel oxide ore.

 ここで、第3の態様において「最大粒子長」とは、ある特定の粒子において、最も長い辺や直径をいう。具体的には、例えば、粒子が楕円状であれば最大粒子長は長径であり、直方体であれば最大粒子長は対角線をいう。図5は、不定形粒子の最大粒子長を示す模式図である。不定形粒子である場合には、図5のように最大粒子長を決定する。この「最大粒子長」は、金属顕微鏡を用いて測定することができる。そして、第3の態様において「平均最大粒子長」とは、無作為に選択した床敷材粒子300個の最大粒子長の平均値をいい、下記式(3)により求められる。
 平均最大粒子長
 =床敷材粒子300個の最大粒子長の総和/300  ・・・(3)
Here, in the third aspect, “maximum particle length” refers to the longest side or diameter of a specific particle. Specifically, for example, if the particle is elliptical, the maximum particle length is a long diameter, and if the particle is a rectangular parallelepiped, the maximum particle length is a diagonal line. FIG. 5 is a schematic diagram showing the maximum particle length of irregular shaped particles. In the case of irregularly shaped particles, the maximum particle length is determined as shown in FIG. This “maximum particle length” can be measured using a metallographic microscope. In the third aspect, the “average maximum particle length” refers to an average value of the maximum particle lengths of 300 randomly selected floor covering particles, and is obtained by the following formula (3).
Average maximum particle length = sum of maximum particle lengths of 300 flooring particles / 300 (3)

 このようにして、特定の床敷材を還元炉の炉床に配置し、その床敷材上に混合物を載置して還元処理を施すことにより、床敷材上に載置する混合物と炉床との反応、及び混合物と床敷材との反応を抑制することができ、高品質のフェロニッケルを製造することができ、また有効に回収することができる。また、床敷材を再利用することにより、製錬のコストを低下させることができる。 In this way, a specific flooring material is placed on the hearth of the reduction furnace, and the mixture placed on the flooring material and the furnace are placed on the flooring material and subjected to reduction treatment. The reaction with the floor and the reaction between the mixture and the flooring material can be suppressed, and high-quality ferronickel can be produced and can be recovered effectively. Moreover, the cost of smelting can be reduced by reusing the flooring material.

 上述したとおり、床敷材としては、その床敷材に含まれる最大粒子長が50.0μm以下の床敷材粒子の数が、床敷材に含まれる総床敷材粒子の数に対し1%以上40%以下であるものを用いる。床敷材に含まれる最大粒子長が50.0μm以下の床敷材粒子の数としては、上述した範囲内に含まれるのであれば特に限定されず、例えば、床敷材に含まれる総床敷材粒子の数に対し、1.2%以上であることが好ましく、1.5%以上であることがより好ましく、1.7%以上であることがさらに好ましく、2%以上であることが特に好ましい。一方で、床敷材に含まれる最大粒子長が50.0μm以下の床敷材粒子の数としては、例えば、床敷材に含まれる総床敷材粒子の数に対し、37%以下であることが好ましく、35%以下であることがより好ましく、32%以下であることがさらに好ましく、30%以下であることが特に好ましい。 As described above, as the flooring material, the number of flooring material particles having a maximum particle length of 50.0 μm or less contained in the flooring material is 1 with respect to the total number of flooring material particles contained in the flooring material. % Or more and 40% or less is used. The number of flooring material particles having a maximum particle length of 50.0 μm or less included in the flooring material is not particularly limited as long as it is included in the above-described range. For example, the total flooring included in the flooring material It is preferably 1.2% or more, more preferably 1.5% or more, still more preferably 1.7% or more, and particularly preferably 2% or more with respect to the number of material particles. preferable. On the other hand, the number of flooring material particles having a maximum particle length of 50.0 μm or less contained in the flooring material is, for example, 37% or less with respect to the total number of flooring material particles contained in the flooring material. It is preferably 35% or less, more preferably 32% or less, and particularly preferably 30% or less.

 また、上述したとおり、床敷材としては、平均最大粒子長が40.0μm以上1050μm以下であるものを用いる。また、平均最大粒子長は、42.0μm以上であることが好ましく、45.0μm以上であることがより好ましく、47.0μm以上であることがさらに好ましく、50.0μm以上であることが特に好ましい。一方で、平均最大粒子長は、1030μm以下であることが好ましく、1000μm以下であることがより好ましい。 Moreover, as described above, as the flooring material, one having an average maximum particle length of 40.0 μm or more and 1050 μm or less is used. The average maximum particle length is preferably 42.0 μm or more, more preferably 45.0 μm or more, further preferably 47.0 μm or more, and particularly preferably 50.0 μm or more. . On the other hand, the average maximum particle length is preferably 1030 μm or less, and more preferably 1000 μm or less.

 床敷材粒子の比表面積としては、特に限定されないが、例えば、0.001μm-1以上であることが好ましく、0.002μm-1以上であることがより好ましく、0.003μm-1以上であることがさらに好ましい。一方で、比表面積としては、例えば、3.0μm-1以下であることが好ましく、2.5μm-1以下であることがより好ましく、2.0μm-1以下であることがさらに好ましい。比表面積がこのような範囲の床敷材を用いることにより、混合物と床敷材の接触面積がより適当なものとなる。なお、「比表面積」は、一般的な比表面積測定装置を用いて測定することができる。 The specific surface area of the bedding material particles is not particularly limited, for example, is preferably 0.001 [mu] m -1 or more, more preferably 0.002 .mu.m -1 or more, is 0.003 .mu.m -1 or More preferably. On the other hand, as the specific surface area, for example, is preferably 3.0 [mu] m -1 or less, more preferably 2.5 [mu] m -1 or less, more preferably 2.0 .mu.m -1 or less. By using a flooring material having a specific surface area in such a range, the contact area between the mixture and the flooring material becomes more appropriate. The “specific surface area” can be measured using a general specific surface area measuring apparatus.

 床敷材としては、特に限定されないが、アルミナ、アルミナセメント、マグネシア、マグネシアセメント、ジルコニア、ジルコニアセメント又はムライトから選択される1種以上の材料から構成されるものを用いることが好ましい。このような床敷材を用いることにより、混合物と炉床との反応及び混合物と床敷材との反応をさらに抑制することができ、高品質のフェロニッケルを製造できる。また、床敷材を再利用することができ、その結果として、製錬のコストを低下させることができる。 The floor covering material is not particularly limited, but it is preferable to use a material composed of one or more materials selected from alumina, alumina cement, magnesia, magnesia cement, zirconia, zirconia cement or mullite. By using such a flooring material, the reaction between the mixture and the hearth and the reaction between the mixture and the flooring material can be further suppressed, and high-quality ferronickel can be produced. Further, the flooring material can be reused, and as a result, the cost of smelting can be reduced.

 混合物の炉床に対する配置率としては、特に限定されないが、例えば、炉床を平面視したときにその炉床の面積の1%以上となるように混合物を配置することが好ましく、1.5%以上となるように混合物を配置することがより好ましく、2%以上となるように混合物を配置することがさらに好ましい。一方で、混合物の炉床に対する配置率としては、炉床の面積の50%以下となるように混合物が配置することが好ましく、45%以下となるように混合物を配置することがより好ましく、42%以下となるように混合物を配置することがさらに好ましく、40%以下となるように混合物を配置することが特に好ましい。 The placement ratio of the mixture with respect to the hearth is not particularly limited. For example, it is preferable to arrange the mixture so that it becomes 1% or more of the area of the hearth when viewed in plan, It is more preferable to arrange the mixture so as to achieve the above, and it is even more preferable to arrange the mixture so as to be 2% or more. On the other hand, as an arrangement ratio of the mixture with respect to the hearth, the mixture is preferably arranged so as to be 50% or less of the area of the hearth, and more preferably, the mixture is arranged so as to be 45% or less. It is more preferable to arrange the mixture so as to be not more than%, and it is particularly preferable to arrange the mixture so as to be not more than 40%.

 (3-4)第4の態様の還元工程
 第4の態様では、床敷材を還元炉の炉床に敷き、その床敷材上に、炉床を平面視したときに炉床の面積の50%以下となるように混合物を配置して、ニッケル酸化鉱石の還元を行う。
(3-4) Reduction process of the fourth aspect In the fourth aspect, the floor covering material is laid on the hearth of the reduction furnace, and when the hearth floor is viewed in plan on the floor covering material, the area of the hearth floor is reduced. The mixture is arranged so as to be 50% or less, and nickel oxide ore is reduced.

 このようにして、床敷材上に特定の配置割合(配置面積率)で混合物を配置させて還元処理を施すことにより、混合物と炉床との反応及び混合物と床敷材との反応を抑制することができ、高品質のフェロニッケルを製造することができ、また有効に回収することができる。また、床敷材を再利用することにより、製錬のコストを低下させることができる。 In this way, the reaction between the mixture and the hearth and the reaction between the mixture and the flooring material are suppressed by placing the mixture on the flooring material at a specific placement ratio (placement area ratio) and performing a reduction treatment. High quality ferronickel can be produced and can be recovered effectively. Moreover, the cost of smelting can be reduced by reusing the flooring material.

 上述したように、還元炉の炉床には、炉床を平面視したときに炉床の面積の50%以下となるように混合物が配置される。還元炉の炉床に、平面視して炉床の面積の50%となるように混合物が配置されることにより、混合物と床敷材との接触面積が適当なものとなる。なお、混合物と床敷材との接触面積が大きすぎると、両者の反応が進行するおそれがある。一方で、接触面積が小さすぎると、生成したスラグやメタルが床敷材の隙間に染み込むおそれがある。 As described above, the mixture is arranged on the hearth of the reduction furnace so that the area of the hearth becomes 50% or less when viewed in plan. By arranging the mixture on the hearth of the reduction furnace so as to be 50% of the area of the hearth in plan view, the contact area between the mixture and the flooring material becomes appropriate. In addition, when the contact area of a mixture and a flooring material is too large, there exists a possibility that reaction of both may advance. On the other hand, if the contact area is too small, the generated slag or metal may penetrate into the gap between the flooring materials.

 また、混合物の炉床に対する配置率(配置面積率)としては、例えば、炉床の面積の3%以上となるように混合物を配置することが好ましく、5%以上となるように混合物を配置することがより好ましい。一方で、還元炉の炉床には、45%以下となるように混合物を配置することが好ましく、42%以下となるように混合物を配置することがより好ましく、40%以下となるように混合物を配置することがさらに好ましい。混合物を、炉床に対しこのような割合の面積で配置することにより、混合物と床敷材の接触面積がより適当なものとなる。 Moreover, as an arrangement ratio (arrangement area ratio) of the mixture with respect to the hearth, for example, the mixture is preferably arranged so as to be 3% or more of the area of the hearth, and the mixture is arranged so as to be 5% or more. It is more preferable. On the other hand, in the hearth of the reduction furnace, the mixture is preferably arranged to be 45% or less, more preferably the mixture is arranged to be 42% or less, and the mixture is made to be 40% or less. It is further preferable to arrange By arranging the mixture in such an area with respect to the hearth, the contact area between the mixture and the flooring material becomes more appropriate.

 ここで、上述したように、炉床には床敷材が敷かれている。この床敷材によって、混合物と炉床とが互いに接触せずに還元処理が施されることになる。図6は、床敷材に対する球状の混合物の設置例を示す模式図である。また、図7は、床敷材に対する直方体状の混合物の設置例を示す模式図である。図6及び図7に示すように、混合物は、少なくともその一部が床敷材上に埋め込まれるようにして設置することが好ましい。混合物を、このようにして設置することにより、混合物を床敷材上に安定的に設置することができ、炉床が動きながら還元反応が進む状況においても転がったり動いたりして反応性にばらつきが生じることを抑制することができる。また、混合物と床敷材との接触面積をある範囲で一定にすることができ、反応性がばらつき難くなる。 Here, as described above, the flooring material is laid on the hearth. By this floor covering material, the reduction treatment is performed without the mixture and the hearth contacting each other. FIG. 6 is a schematic diagram showing an installation example of a spherical mixture with respect to a flooring material. FIG. 7 is a schematic diagram showing an installation example of a rectangular parallelepiped mixture with respect to the flooring material. As shown in FIG.6 and FIG.7, it is preferable to install the mixture so that at least a part thereof is embedded on the flooring material. By installing the mixture in this way, the mixture can be stably installed on the flooring material, and even when the reduction reaction proceeds while the hearth moves, the reactivity varies due to rolling or moving. Can be prevented from occurring. Further, the contact area between the mixture and the flooring material can be made constant within a certain range, and the reactivity is difficult to vary.

 床敷材の形状としては、特に限定されないが、粒子から構成されるもの(床敷材粒子)を用いることが好ましい。床敷材として粒子から構成されるものを用いることにより、混合物と床敷材との接触面積がより適当なものとなり、また、炉床に敷き詰める際の操作性や、炉床から回収する際の取り扱い性にも優れる。 The shape of the flooring material is not particularly limited, but it is preferable to use particles composed of particles (flooring material particles). By using particles composed of particles as the flooring material, the contact area between the mixture and the flooring material becomes more appropriate, and the operability when laying on the hearth and when recovering from the hearth Excellent handleability.

 床敷材として、粒子から構成されるものを用いる場合、床敷材粒子の比表面積としては、特に限定されないが、例えば、0.001μm-1以上であることが好ましく、0.002μm-1以上であることがより好ましく、0.003μm-1以上であることがさらに好ましい。一方で、比表面積としては、例えば、3.0μm-1以下であることが好ましく、2.5μm-1以下であることがより好ましく、2.0μm-1以下であることがさらに好ましい。比表面積がこのような範囲の床敷材を用いることにより、混合物と床敷材の接触面積がより適当なものとなる。なお、「比表面積」は、一般的な比表面積測定装置を用いて測定することができる。 As bedding material, if used those composed of particles, the specific surface area of the bedding material particles is not particularly limited, for example, is preferably 0.001 [mu] m -1 or more, 0.002 .mu.m -1 or More preferably, it is 0.003 μm −1 or more. On the other hand, as the specific surface area, for example, is preferably 3.0 [mu] m -1 or less, more preferably 2.5 [mu] m -1 or less, more preferably 2.0 .mu.m -1 or less. By using a flooring material having a specific surface area in such a range, the contact area between the mixture and the flooring material becomes more appropriate. The “specific surface area” can be measured using a general specific surface area measuring apparatus.

 また、床敷材として粒子から構成されるものを用いる場合、その床敷材粒子の大きさとしては特に限定されないが、例えば、平均最大粒子長が20.0μm以上1000μm以下であることが好ましく、50.0μm以上700μm以下であることがより好ましい。床敷材の平均最大粒子長がこのような範囲にあることにより、混合物と床敷材の接触面積がより適当なものとなる。 In addition, when using what is composed of particles as the flooring material, the size of the flooring material particles is not particularly limited, for example, the average maximum particle length is preferably 20.0 μm or more and 1000 μm or less, More preferably, it is 50.0 μm or more and 700 μm or less. When the average maximum particle length of the flooring material is in such a range, the contact area between the mixture and the flooring material becomes more appropriate.

 ここで、第4の態様において「最大粒子長」とは、ある特定の粒子において、最も長い辺や直径をいう。具体的には、例えば、粒子が楕円状であれば最大粒子長は長径であり、直方体であれば最大粒子長は対角線をいう。この「最大粒子長」は、金属顕微鏡を用いて測定することができる。そして、第4の態様において「平均最大粒子長」は、無作為に選定した床敷材粒子100個の最大粒子長の平均値である。 Here, in the fourth aspect, “maximum particle length” refers to the longest side or diameter of a specific particle. Specifically, for example, if the particle is elliptical, the maximum particle length is a long diameter, and if the particle is a rectangular parallelepiped, the maximum particle length is a diagonal line. This “maximum particle length” can be measured using a metallographic microscope. In the fourth embodiment, the “average maximum particle length” is an average value of the maximum particle lengths of 100 randomly selected flooring material particles.

 また、床敷材としては、特に限定されないが、アルミナ、アルミナセメント、マグネシア、マグネシアセメント、ジルコニア、ジルコニアセメント及びムライトから選択される1種以上の材料から構成されるものを用いることが好ましい。このような床敷材を用いることにより、混合物と炉床との反応及び混合物と床敷材との反応をさらに抑制することができ、高品質のフェロニッケルを製造できる。また、床敷材を再利用することができ、その結果として、製錬のコストを低下させることができる。 Further, the floor covering material is not particularly limited, but it is preferable to use a material composed of one or more materials selected from alumina, alumina cement, magnesia, magnesia cement, zirconia, zirconia cement and mullite. By using such a flooring material, the reaction between the mixture and the hearth and the reaction between the mixture and the flooring material can be further suppressed, and high-quality ferronickel can be produced. Further, the flooring material can be reused, and as a result, the cost of smelting can be reduced.

 (3-5)その他の条件
 以下、第1~第4の態様の還元工程において共通する還元条件や共通で使用する還元炉について説明する。
(3-5) Other Conditions Hereinafter, reduction conditions common to the reduction processes of the first to fourth aspects and reduction furnaces used in common will be described.

 還元炉を使用した還元処理においては、ニッケル酸化鉱石に含まれる金属酸化物である酸化ニッケルは可能な限り完全に、且つ鉄に対して優先的に還元し、一方で、ニッケル酸化鉱石と共に原料粉末として混合した鉄鉱石等に由来する酸化鉄は一部だけ還元して、目的とするニッケル品位のフェロニッケルが得られる、いわゆる部分還元を行うことが好ましい。 In the reduction treatment using a reduction furnace, nickel oxide, which is a metal oxide contained in nickel oxide ore, is reduced as completely as possible and preferentially to iron, while raw powder together with nickel oxide ore. It is preferable to carry out so-called partial reduction, in which iron oxide derived from iron ore and the like mixed is partially reduced to obtain ferronickel having a target nickel quality.

 具体的に、還元温度としては、特に限定されないが、1200℃以上1450℃以下の範囲とすることが好ましく、1300℃以上1400℃以下の範囲とすることがより好ましい。このような温度範囲で還元することによって、均一に還元反応を生じさせることができ、品質のばらつきを抑制したメタル(フェロニッケルメタル)を生成させることができる。またより好ましくは1300℃以上1400℃以下の範囲の還元温度で還元することで、比較的短時間で所望の還元反応を生じさせることができる。 Specifically, the reduction temperature is not particularly limited, but is preferably in the range of 1200 ° C to 1450 ° C, and more preferably in the range of 1300 ° C to 1400 ° C. By reducing in such a temperature range, a reduction reaction can be caused uniformly and a metal (ferronickel metal) with suppressed quality variation can be generated. More preferably, by performing reduction at a reduction temperature in the range of 1300 ° C. or higher and 1400 ° C. or lower, a desired reduction reaction can be caused in a relatively short time.

 通常、金属製の炉床を有する還元炉を用いて1300℃以上の高温で還元した場合、混合物から生成したスラグやメタルが、炉床と反応し、炉床を短時間で損傷することがある。また、混合物中又は還元されたメタルに炉床の金属成分等が混入し、得られるメタルの品質の低下を起こすおそれもある。さらに、例えば石炭やコークス等、通常の床敷材を用いた場合、混合物から生成したスラグやメタルが、このような床敷材と反応するおそれもある。このような反応は、僅かな程度であれば許容できるが、床敷材が変質し再利用できないこともある。 Usually, when reduction is performed at a high temperature of 1300 ° C. or higher using a reduction furnace having a metal hearth, the slag or metal generated from the mixture may react with the hearth and damage the hearth in a short time. . Moreover, the metal component of a hearth etc. may mix in the mixture or the reduced metal, and there exists a possibility of causing the fall of the quality of the metal obtained. Furthermore, when usual floor covering materials, such as coal and coke, are used, there exists a possibility that the slag and metal produced | generated from the mixture may react with such floor covering materials. Such a reaction is acceptable to a slight extent, but the flooring material may be altered and cannot be reused.

 還元処理に際しては、上述した範囲の還元温度になるまで還元炉における還元室の内部温度を上昇させ、昇温後にその温度を維持する。 During the reduction treatment, the internal temperature of the reduction chamber in the reduction furnace is raised until the reduction temperature in the above-described range, and the temperature is maintained after the temperature rise.

  [回転炉床炉]
 上述したとおり、還元炉としては、例えば移動式炉床炉又は回転炉床炉を用いることができる。このような還元炉によれば、金属酸化物中に含まれる金属を効果的にメタル化して、しかも効率的な製錬処理を行うことができる。以下、還元炉の一例として、回転炉床炉の構成について、図3を用いて説明する。
[Rotating hearth furnace]
As described above, as the reduction furnace, for example, a mobile hearth furnace or a rotary hearth furnace can be used. According to such a reduction furnace, the metal contained in the metal oxide can be effectively metalized and an efficient smelting treatment can be performed. Hereinafter, the configuration of a rotary hearth furnace will be described with reference to FIG. 3 as an example of a reduction furnace.

 図3は、炉床が回転する回転炉床炉の構成例を示す図(平面図)である。図3に示すように、回転炉床炉1は、炉床が回転する領域10を有し、領域10は4つ分割されてそれぞれで処理室(10a,10b,10c,10d)を構成している。具体的に、この回転炉床炉1においては、例えば、符号「10a」~「10d」の4つすべての処理室を、還元処理を行う還元室とすることができる。また、還元工程S33における処理の後に後述する温度保持工程S34を実行する場合には、例えば、処理室「10a」、「10b」、「10c」を還元室とし、処理室「10d」を温度保持工程S34における処理を行う温度保持室とすることができる。さらに、還元工程S33における処理の後に後述する冷却工程S5を実行する場合には、例えば、処理室「10a」、「10b」、「10c」を還元室とし、処理室「10d」を冷却工程S5における処理を行う温度保持室とすることができる。 FIG. 3 is a diagram (plan view) showing a configuration example of a rotary hearth furnace in which the hearth rotates. As shown in FIG. 3, the rotary hearth furnace 1 has a region 10 in which the hearth rotates, and the region 10 is divided into four, and each constitutes a processing chamber (10a, 10b, 10c, 10d). Yes. Specifically, in the rotary hearth furnace 1, for example, all four treatment chambers with reference numerals “10a” to “10d” may be reduction chambers for performing reduction treatment. Further, when the temperature holding step S34 described later is executed after the processing in the reduction step S33, for example, the processing chambers “10a”, “10b”, and “10c” are set as the reduction chamber, and the processing chamber “10d” is held at the temperature. It can be set as the temperature holding chamber which performs the process in process S34. Further, when the cooling step S5 described later is performed after the processing in the reduction step S33, for example, the processing chambers “10a”, “10b”, and “10c” are set as the reduction chamber, and the processing chamber “10d” is set as the cooling step S5. It can be set as the temperature holding chamber which performs the process in.

 各工程間、すなわち各処理室間は、反応温度を厳密に制御してエネルギーロスを抑制するために、仕切り壁で仕切られた構成とすることが好ましい。このように、各工程の亜大を仕切ることが可能な構造を有する回転炉床炉によれば、後述するように、還元工程S33における処理と温度保持工程S34における処理とを、エネルギーロスを抑制しながら、同一の回転炉床炉を用いて行うことができる。ただし、仕切り壁が固定式のものであると、工程間の搬送や、特に回転炉床炉への装入及び排出が困難となる可能性があるため、その仕切り壁としては、処理物の移動に差し支えることがない程度に開閉できる構造とすることが好ましい。 It is preferable that each process, that is, between each processing chamber, be partitioned by a partition wall in order to strictly control the reaction temperature and suppress energy loss. Thus, according to the rotary hearth furnace having a structure capable of partitioning the sub-size of each process, the energy loss is suppressed between the process in the reduction process S33 and the process in the temperature holding process S34, as will be described later. However, the same rotary hearth furnace can be used. However, if the partition wall is of a fixed type, it may be difficult to transport between processes, and particularly to charge and discharge the rotary hearth furnace. It is preferable to have a structure that can be opened and closed to the extent that it does not interfere with.

 なお、炉床が回転する領域10を分割して形成される処理室の数としては、図3に例示する4つに限られるものではない。また、還元室の数や温度保持室の数についても、上述した例に限られず、処理時間等に応じて適宜設定することができる。 Note that the number of processing chambers formed by dividing the area 10 in which the hearth rotates is not limited to four illustrated in FIG. Further, the number of reduction chambers and the number of temperature holding chambers are not limited to the above-described example, and can be appropriately set according to the processing time and the like.

 回転炉床炉1は、上述したように、平面上に回転移動する炉床を備えており、混合物を載置した炉床が所定の速度で回転移動することで、それぞれの処理室(10a,10b,10c,10d)を通過し、その通過の際に処理が行われる。なお、図3中の回転炉床炉1上の矢印は、炉床の回転方向を示すとともに、処理物(混合物)の移動方向を示す。 As described above, the rotary hearth furnace 1 includes a hearth that rotates and moves on a plane, and the hearth on which the mixture is placed rotates and moves at a predetermined speed, so that each processing chamber (10a, 10a, 10b, 10c, 10d), and processing is performed at the time of the passage. In addition, while the arrow on the rotary hearth furnace 1 in FIG. 3 shows the rotation direction of a hearth, it shows the moving direction of a processed material (mixture).

 また、回転炉床炉1は、その炉外に設けられた乾燥室20と、予熱室30とが接続されており、上述したように、乾燥室20にて混合物に対する乾燥処理が施されたのち、乾燥後の混合物が予熱室30に移動して予熱処理され、予熱処理後の混合物が回転炉床炉1内に順次移されるようになっている。また、回転炉床炉1は、その炉外に設けられた冷却室40が接続されており、還元室又は温度保持室(10d)を経て得られた還元物がその冷却室40にて冷却処理される(後述する冷却工程S35)。 Further, the rotary hearth furnace 1 is connected to a drying chamber 20 provided outside the furnace and a preheating chamber 30, and as described above, after the drying treatment is performed on the mixture in the drying chamber 20. The dried mixture moves to the preheating chamber 30 and is preheated, and the preheated mixture is sequentially transferred into the rotary hearth furnace 1. In addition, the rotary hearth furnace 1 is connected to a cooling chamber 40 provided outside the furnace, and the reduced product obtained through the reduction chamber or the temperature holding chamber (10d) is cooled in the cooling chamber 40. (Cooling step S35 described later).

 (4)温度保持工程
 還元工程S33を経て得られた還元物を、回転炉床炉内で所定の高い温度条件で保持する温度保持工程S34を行うようにしてもよい。このように、還元工程S33における所定の還元温度での還元処理により得られた還元物を、すぐに冷却するのではなく、高温の雰囲気で保持することによって、還元物中において生成したメタル成分を沈降、粗大化させることができる。
(4) Temperature holding process You may make it perform the temperature holding process S34 which hold | maintains the reduced material obtained through reduction process S33 on a predetermined high temperature condition in a rotary hearth furnace. In this way, the reduced product obtained by the reduction treatment at the predetermined reduction temperature in the reduction step S33 is not immediately cooled, but is held in a high-temperature atmosphere, so that the metal component generated in the reduced product is retained. It can be settled and coarsened.

 なお、温度保持工程S34においても、床敷材を用いることによって、還元反応によりニッケルメタルやスラグが生成しても、炉床と反応せず、スラグが炉床に染み込んだり、貼り付いたりしない。 In the temperature holding step S34, even when nickel metal or slag is generated by a reduction reaction by using a flooring material, it does not react with the hearth, and the slag does not penetrate or stick to the hearth.

 還元処理して得られた状態において還元物中のメタル成分が小さい場合、例えば200μm以下程度のバルク状のメタルであった場合には、その後の分離工程S4にてメタルとスラグとを分離することが困難になってしまう。このため、必要に応じて、還元物を高温保持することによって、還元物中のスラグよりも比重の大きいメタルを沈降、凝集させて、メタルを粗大化させる。 When the metal component in the reduced product is small in the state obtained by the reduction treatment, for example, when it is a bulk metal of about 200 μm or less, the metal and slag are separated in the subsequent separation step S4. Will become difficult. For this reason, if necessary, the reduced product is kept at a high temperature, so that the metal having a specific gravity larger than that of the slag in the reduced product is settled and aggregated to coarsen the metal.

 なお、還元工程S33における還元処理により、製造上問題ないレベルまでメタルが粗大化している場合には、特にこの温度保持工程S34を設けることを必要としない。 In addition, when the metal is coarsened to a level at which there is no problem in manufacturing due to the reduction process in the reduction step S33, it is not particularly necessary to provide the temperature holding step S34.

 具体的に、温度保持工程S34における還元物の保持温度としては、1300℃以上1500℃以下の高温範囲とすることが好ましい。このような範囲で還元物を高温保持することによって、還元物中のメタル成分を効率よく沈降させて粗大なメタルとすることができる。なお、保持温度が1300℃未満であると、還元物の多くの部分が固相となるため、メタル成分が沈降しないか、沈降した場合であっても時間を要する。一方で、保持温度が1500℃を超えると、得られた還元物と床敷材との反応が進行して、還元物を回収できなくなることがあり、また、炉を損傷させてしまうことがある。 Specifically, the reduced product holding temperature in the temperature holding step S34 is preferably in the high temperature range of 1300 ° C to 1500 ° C. By holding the reduced product at a high temperature in such a range, the metal component in the reduced product can be efficiently precipitated to form a coarse metal. When the holding temperature is lower than 1300 ° C., a large part of the reduced product becomes a solid phase, so that it takes time even when the metal component does not settle or settles. On the other hand, when the holding temperature exceeds 1500 ° C., the reaction between the obtained reduced product and the flooring material proceeds and the reduced product may not be recovered, and the furnace may be damaged. .

 ここで、温度保持工程S34における処理は、還元工程S33にて使用する回転炉床炉1内において、還元処理に続いて連続的に行うようにする。すなわち、図3を用いて説明したように、回転炉床炉1において、例えば、処理室「10a」、「10b」、「10c」を還元室とし、処理室「10d」を温度保持工程S34における処理を行う温度保持室とし、還元室(10a、10b、10c)を通過して得られた還元物を、温度保持室(10d)にて所定の温度範囲に保持させる。 Here, the treatment in the temperature holding step S34 is performed continuously following the reduction treatment in the rotary hearth furnace 1 used in the reduction step S33. That is, as described with reference to FIG. 3, in the rotary hearth furnace 1, for example, the processing chambers “10a”, “10b”, and “10c” are used as the reduction chambers, and the processing chamber “10d” is used in the temperature holding step S34. A temperature holding chamber for processing is used, and the reduced product obtained through the reduction chambers (10a, 10b, 10c) is held in a predetermined temperature range in the temperature holding chamber (10d).

 このように、還元処理を経て得られた還元物を所定の温度に保持する処理を、回転炉床炉1を用いて連続的に行うことによって、還元物中のメタル成分を効率的に沈降させて粗大化させることができる。しかも、還元工程S33における処理と、温度保持工程S34における処理とを別々の炉ではなく、回転炉床炉1を用いて連続的に行うことで、各処理間におけるヒートロスを低減して効率的な操業を可能にする。 Thus, the metal component in the reduction product is efficiently settled by continuously performing the process of maintaining the reduction product obtained through the reduction treatment at a predetermined temperature using the rotary hearth furnace 1. Can be coarsened. In addition, the process in the reduction process S33 and the process in the temperature holding process S34 are continuously performed using the rotary hearth furnace 1 instead of separate furnaces, so that heat loss between the processes is reduced and efficient. Enable operation.

 (5)冷却工程
 冷却工程S35では、還元工程S33を経て得られた還元物、または温度保持工程S34にて所定の時間に亘り高温保持した後の還元物を、続く分離工程S4にて分離回収できる温度まで冷却する。
(5) Cooling step In the cooling step S35, the reduction product obtained through the reduction step S33 or the reduction product after being held at a high temperature for a predetermined time in the temperature holding step S34 is separated and recovered in the subsequent separation step S4. Cool down to a temperature where you can.

 冷却工程S35は、上述したように得られた還元物を冷却する工程であるため、回転炉床炉1の炉外に接続された冷却室にて行うことが好ましい。なお、図3に、回転炉床炉1に接続された冷却室40の構成例を示すが、この冷却室40は回転炉床炉1の炉外に接続して設けられている。このように、回転炉床炉1の炉外に設けられた冷却室40にて冷却処理を行うことによって、回転炉床炉1の内部温度の低下を防ぐことができ、エネルギーロスを抑えることができる。これにより、効率的なフェロニッケルの生産を可能とする。 Since the cooling step S35 is a step of cooling the reduction product obtained as described above, it is preferably performed in a cooling chamber connected to the outside of the rotary hearth furnace 1. FIG. 3 shows a configuration example of the cooling chamber 40 connected to the rotary hearth furnace 1. The cooling chamber 40 is provided outside the rotary hearth furnace 1. Thus, by performing the cooling process in the cooling chamber 40 provided outside the rotary hearth furnace 1, a decrease in the internal temperature of the rotary hearth furnace 1 can be prevented and energy loss can be suppressed. it can. This enables efficient production of ferronickel.

 冷却工程S35における温度(以下、「回収時温度」ともいう)は、還元物が実質的に固体として扱える温度であって、できるだけ高い温度であることが好ましい。回収時温度をできるだけ高くすることにより、回転移動する回転炉床炉1の炉床が、予熱工程S32を実行する予熱室30との接続箇所に戻ったときでもエネルギーロスを低減でき、再加熱に要するエネルギーをより一層節約することができる。 The temperature in the cooling step S35 (hereinafter also referred to as “recovery temperature”) is a temperature at which the reduced product can be handled substantially as a solid, and is preferably as high as possible. By making the temperature at the time of recovery as high as possible, energy loss can be reduced even when the hearth of the rotary hearth furnace 1 that rotates and moves back to the connection point with the preheating chamber 30 that executes the preheating step S32, and reheating is possible. The required energy can be further saved.

 具体的に、回収時温度としては600℃以上とすることが好ましい。このように回収時温度を高い温度にすることによって、再加熱に要するエネルギーを大幅に削減でき、低コストで効率的な製錬処理を行うことができる。また、回転炉床炉1の内部における温度差の減少することによって、その炉床や炉壁等に加わる熱応力を減少させることができ、回転炉床炉1の寿命を大きく延ばすことができる。さらに、操業中の不具合も大幅に減らすことができる。 Specifically, the recovery temperature is preferably 600 ° C. or higher. Thus, by making the temperature at the time of recovery high, the energy required for reheating can be greatly reduced, and efficient smelting treatment can be performed at low cost. Moreover, by reducing the temperature difference in the rotary hearth furnace 1, the thermal stress applied to the hearth, the furnace wall, etc. can be reduced, and the life of the rotary hearth furnace 1 can be greatly extended. In addition, problems during operation can be greatly reduced.

 <2-4.分離工程>
 分離工程S4は、還元処理工程S3にて生成した還元物からメタル(フェロニッケルメタル)を分離し回収する。具体的に、分離工程S4では、混合物を還元加熱処理することによって得られた、メタル相(メタル固相)とスラグ相(スラグ固相)とが混在する混在物(還元物)から、メタル相を分離して回収する。
<2-4. Separation process>
Separation process S4 isolate | separates and collect | recovers a metal (ferronickel metal) from the reduced material produced | generated in reduction process process S3. Specifically, in the separation step S4, a metal phase obtained from a mixture (reduced product) of a metal phase (metal solid phase) and a slag phase (slag solid phase) obtained by subjecting the mixture to reduction heat treatment is used. Is separated and recovered.

 固体として得られたメタル相とスラグ相との混在物からメタル相とスラグ相とを分離する方法としては、例えば、篩い分けによる不要物の除去に加えて、比重による分離や、磁力による分離等の方法を利用することができる。また、得られたメタル相とスラグ相は、濡れ性が悪いことから容易に分離することができ、大きな混在物に対して、例えば、所定の落差を設けて落下させる、あるいは篩い分けの際に所定の振動を与える等の衝撃を与えることで、その混在物からメタル相とスラグ相とを容易に分離することができる。 As a method for separating the metal phase and the slag phase from the mixture of the metal phase and the slag phase obtained as a solid, for example, in addition to removing unnecessary materials by sieving, separation by specific gravity, separation by magnetic force, etc. Can be used. In addition, the obtained metal phase and slag phase can be easily separated because of poor wettability, and for example, when a large mixture is dropped with a predetermined drop, or when sieving By giving an impact such as giving a predetermined vibration, the metal phase and the slag phase can be easily separated from the mixture.

 このようにしてメタル相とスラグ相とを分離することによって、メタル相を回収し、フェロニッケルの製品とすることができる。 Thus, by separating the metal phase and the slag phase, the metal phase can be recovered and made into a ferronickel product.

 以下、本発明の実施例を示してより具体的に説明するが、本発明は以下の実施例に何ら限定されるものではない。 Hereinafter, although an example of the present invention is shown and explained more concretely, the present invention is not limited to the following example at all.

〔実施例1〕
 (混合処理工程)
 原料の酸化鉱石としてのニッケル酸化鉱石と、鉄鉱石と、フラックス成分である珪砂及び石灰石と、バインダーと、炭素質還元剤である石炭とを、適量の水を添加しながら混合機を用いて混合して混合物を得た。なお、炭素質還元剤は、酸化ニッケルと酸化鉄(Fe)とを過不足なくメタルに還元するのに必要な化学当量の合計値を100%としたときに、炭素量で30%に相当する分量で含有させた。
[Example 1]
(Mixing process)
Mix nickel oxide ore as raw material oxide ore, iron ore, silica sand and limestone as flux components, binder and coal as carbonaceous reducing agent using a mixer while adding appropriate amount of water. To obtain a mixture. The carbonaceous reducing agent is 30% in terms of carbon when the total value of chemical equivalents required for reducing nickel oxide and iron oxide (Fe 2 O 3 ) to metal without excess or deficiency is 100%. In an amount corresponding to.

 そして、混合機によって混合して得られた混合物を、二軸混練機によって混練した。 The mixture obtained by mixing with a mixer was kneaded with a twin-screw kneader.

 (還元投入前処理工程)
 次に、混練して得られた混合物試料を、パン型造粒機を用いてφ18±1.5mmの球状のペレットに成形した。
(Reduction input pretreatment process)
Next, the mixture sample obtained by kneading was formed into spherical pellets of φ18 ± 1.5 mm using a pan-type granulator.

 (還元処理工程)
 次に、図3に例示したような回転炉床炉1を用いて、混合物試料を用いて処理条件を変えて還元処理を行った。回転炉床炉1としては、図3に示すように、領域10の外に、ペレットを乾燥する乾燥室20と、乾燥室20に連続して設けられた予熱室30と、炉内における処理室10a~10dを経て得られた還元物を冷却する冷却室40とが接続されているものを用いた。なお、実施例1においては、処理室10dを冷却室として用いた。
(Reduction treatment process)
Next, using the rotary hearth furnace 1 illustrated in FIG. 3, reduction treatment was performed by changing the treatment conditions using the mixture sample. As shown in FIG. 3, the rotary hearth furnace 1 includes a drying chamber 20 for drying pellets, a preheating chamber 30 provided continuously to the drying chamber 20, and a processing chamber in the furnace, as shown in FIG. 3. What connected with the cooling chamber 40 which cools the reduced material obtained through 10a-10d was used. In Example 1, the processing chamber 10d was used as a cooling chamber.

 具体的には、ペレット試料を、回転炉床炉1の炉外に接続された乾燥室20に装入し、乾燥処理を施した。乾燥処理は、実質的に酸素を含まない窒素雰囲気中において、ペレット中を固形分が70重量%程度、水分が30重量%程度となるように、250℃~350℃の熱風をペレットに吹き付けることによって行った。下記表3に、乾燥処理後のペレットの固形分組成(炭素を除く)を示す。 Specifically, the pellet sample was placed in the drying chamber 20 connected to the outside of the rotary hearth furnace 1 and dried. In the drying process, hot air of 250 ° C. to 350 ° C. is blown onto the pellets in a nitrogen atmosphere that does not substantially contain oxygen so that the pellets have a solid content of about 70% by weight and water content of about 30% by weight. Went by. Table 3 below shows the solid content composition (excluding carbon) of the pellets after the drying treatment.

 続いて、乾燥処理後のペレットを、乾燥室20に連続して設けられた予熱室30に移行させ、予熱室30内の温度を700℃以上1280℃以下の範囲に保持して、ペレットに対する予熱処理を行った。 Subsequently, the pellets after the drying treatment are transferred to a preheating chamber 30 continuously provided in the drying chamber 20, and the temperature in the preheating chamber 30 is maintained in a range of 700 ° C. or higher and 1280 ° C. or lower, so Heat treatment was performed.

 続いて、予熱処理後のペレットを、回転炉床炉1の内部に移行させて還元処理及び温度保持処理を行った。具体的に、回転炉床炉1としては、炉床が回転移動する領域10を4分割して4つの処理室を備えるものとし、4つの処理室10a~10dをいずれも還元処理を実行する還元室とした。 Subsequently, the pellets after the pre-heat treatment were transferred into the rotary hearth furnace 1 and subjected to reduction treatment and temperature holding treatment. Specifically, as the rotary hearth furnace 1, the region 10 in which the hearth rotates and moves is divided into four, and four processing chambers are provided, and all the four processing chambers 10a to 10d perform reduction processing. The room.

 還元処理を経て得られた還元物については、回転炉床炉1に接続された冷却室に移行させ、窒素を流しながら速やかに室温まで冷却して大気中へ取り出した。なお、還元物の回転炉床炉1からの回収は、冷却室40に還元物を移行させる形態で行い、冷却室40に設置したガイドによって還元物を沿わせるようにして回収した。 The reduced product obtained through the reduction treatment was transferred to a cooling chamber connected to the rotary hearth furnace 1 and quickly cooled to room temperature while flowing nitrogen and taken out into the atmosphere. The reductant was recovered from the rotary hearth furnace 1 in a form in which the reductant was transferred to the cooling chamber 40, and the reductant was recovered along with a guide installed in the cooling chamber 40.

 実施例1-1~1-48においては、粒子から構成される床敷材を炉床に敷き、その上に混合物のペレットを置いて還元処理を行った。比較例1-1~1-3においては、金属製の炉床の上に、直接ペレットを置いて還元処理を行った。下記表4~6に、実施例1~48及び比較例1-1~1-3の還元工程における還元処理の条件を示す。 In Examples 1-1 to 1-48, a flooring material composed of particles was laid on the hearth, and a pellet of the mixture was placed thereon to perform a reduction treatment. In Comparative Examples 1-1 to 1-3, the reduction treatment was performed by placing the pellets directly on the metal hearth. Tables 4 to 6 below show the conditions for the reduction treatment in the reduction steps of Examples 1 to 48 and Comparative Examples 1-1 to 1-3.

 平均最大粒子長は、金属顕微鏡を用いて、無作為に選定し測定した床敷材粒子300個の最大粒子長の平均値より求めた。また、床敷材の体積は、最大粒子長の平均値を求めるのに用いた粒子300個の総重量を測定し、床敷材を構成する材料の密度で割ることにより粒子300個の総体積を求めた。 The average maximum particle length was obtained from the average value of the maximum particle lengths of 300 floor covering particles randomly selected and measured using a metal microscope. Further, the volume of the flooring material is determined by measuring the total weight of 300 particles used to obtain the average value of the maximum particle length and dividing by the density of the material constituting the flooring material. Asked.

 還元処理後のペレット、床敷材及び炉床を目視で確認し、相互の反応の有無を確認した。その結果を下記表4~6に示す。 After the reduction treatment, the pellets, floor covering material, and hearth were visually confirmed to confirm the presence or absence of mutual reaction. The results are shown in Tables 4-6 below.

 また、取り出した試料のニッケル品位をICP発光分光分析器(SHIMAZU S-8100)により分析し、ニッケルメタル率とメタル中ニッケル含有率とをそれぞれ算出した。なお、ニッケルメタル率は、下記(4)式により、メタル中ニッケル含有率は下記(5)式により、それぞれ算出した。下記表4~6に、実施例1-1~1-48及び比較例1-1~1-3により得られた試料のニッケルメタル率及びメタル中ニッケル含有率を示す。
 ニッケルメタル化率=還元処理投入ペレット中のメタル化したNiの量/(還元処理投入ペレット中の全てのNi量)×100(%) ・・・(4)
 メタル中ニッケル含有率=還元処理投入ペレット中のメタル化したNiの量/(還元処理投入ペレット中のメタルしたNiとFeの合計量)×100(%)  ・・・(5)
Further, the nickel quality of the sample taken out was analyzed with an ICP emission spectroscopic analyzer (SHIMAZU S-8100), and the nickel metal ratio and the nickel content in the metal were calculated. The nickel metal ratio was calculated by the following formula (4), and the nickel content in the metal was calculated by the following formula (5). Tables 4 to 6 below show the nickel metal ratio and the nickel content in the metal of the samples obtained in Examples 1-1 to 1-48 and Comparative Examples 1-1 to 1-3.
Nickel metalization rate = amount of Ni metalized in the reduction treatment input pellet / (total amount of Ni in the reduction treatment input pellet) × 100 (%) (4)
Nickel content in metal = amount of Ni metalized in the reduction treatment input pellet / (total amount of metal Ni and Fe in the reduction treatment input pellet) × 100 (%) (5)

Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004

Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005

Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006

 このように、実施例1-1~1-48においては、所定の床敷材を用いたことにより、床敷材や炉床と試料が反応することなく、その結果、不純物等の少ない高品質のフェロニッケルを製造することができた。また、床敷材が再利用できるため、低コストで実現し得る。さらに、メタル成分が多いためにメタルの粗大化が生じやすい。 As described above, in Examples 1-1 to 1-48, the predetermined flooring material was used, so that the flooring material and the hearth did not react with the sample, and as a result, high quality with less impurities and the like. Of ferronickel could be produced. Further, since the flooring material can be reused, it can be realized at a low cost. Furthermore, since the metal component is large, the metal is likely to become coarse.

 これに対し、比較例1-1~1-3は、試料が炉床と反応し、混じり合い、有効にメタルを回収することができなかった。 On the other hand, in Comparative Examples 1-1 to 1-3, the sample reacted with the hearth and mixed, and the metal could not be recovered effectively.

〔実施例2〕
 (混合処理工程)
 原料の酸化鉱石としてのニッケル酸化鉱石と、鉄鉱石と、フラックス成分である珪砂及び石灰石と、バインダーと、炭素質還元剤である石炭とを、適量の水を添加しながら混合機を用いて混合して混合物を得た。なお、炭素質還元剤は、酸化ニッケルと酸化鉄(Fe)とを過不足なくメタルに還元するのに必要な化学当量の合計値を100%としたときに、炭素量で36%に相当する分量で含有させた。
[Example 2]
(Mixing process)
Mix nickel oxide ore as raw material oxide ore, iron ore, silica sand and limestone as flux components, binder and coal as carbonaceous reducing agent using a mixer while adding appropriate amount of water. To obtain a mixture. The carbonaceous reducing agent is 36% in terms of carbon amount when the total value of chemical equivalents required to reduce nickel oxide and iron oxide (Fe 2 O 3 ) to metal without excess or deficiency is 100%. In an amount corresponding to.

 そして、混合機によって混合して得られた混合物を、二軸混練機によって混練した。 The mixture obtained by mixing with a mixer was kneaded with a twin-screw kneader.

 (還元投入前処理工程)
 次に、混練して得られた混合物試料を、パン型造粒機を用いてφ16±1.5mmの球状のペレットに成形した。
(Reduction input pretreatment process)
Next, the mixture sample obtained by kneading was molded into spherical pellets of φ16 ± 1.5 mm using a pan-type granulator.

 (還元処理工程)
 次に、図3に例示したような回転炉床炉1を用い、その回転炉床炉1の炉床に、粒子から構成される床敷材を敷き、混合物試料を用いて処理条件を変えて還元処理を行った。回転炉床炉1としては、図3に示すように、領域10の外に、ペレットを乾燥する乾燥室20と、乾燥室20に連続して設けられた予熱室30と、炉内における処理室10a~10dを経て得られた還元物を冷却する冷却室40とが接続されているものを用いた。なお、実施例2においては、処理室10dを冷却室として用いた。
(Reduction treatment process)
Next, using the rotary hearth furnace 1 illustrated in FIG. 3, the flooring material composed of particles is laid on the hearth of the rotary hearth furnace 1, and the processing conditions are changed using the mixture sample. Reduction treatment was performed. As shown in FIG. 3, the rotary hearth furnace 1 includes a drying chamber 20 for drying pellets, a preheating chamber 30 provided continuously to the drying chamber 20, and a processing chamber in the furnace, as shown in FIG. 3. What connected with the cooling chamber 40 which cools the reduced material obtained through 10a-10d was used. In Example 2, the processing chamber 10d was used as a cooling chamber.

 具体的には、ペレット試料を、回転炉床炉1の炉外に接続された乾燥室20に装入し、乾燥処理を施した。乾燥処理は、実質的に酸素を含まない窒素雰囲気中において、ペレット中を固形分が70重量%程度、水分が30重量%程度となるように、250℃~350℃の熱風をペレットに吹き付けることによって行った。下記表7に、乾燥処理後のペレットの固形分組成(炭素を除く)を示す。 Specifically, the pellet sample was placed in the drying chamber 20 connected to the outside of the rotary hearth furnace 1 and dried. In the drying process, hot air of 250 ° C. to 350 ° C. is blown onto the pellets in a nitrogen atmosphere that does not substantially contain oxygen so that the pellets have a solid content of about 70% by weight and water content of about 30% by weight. Went by. Table 7 below shows the solid content composition (excluding carbon) of the pellets after the drying treatment.

Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007

 続いて、乾燥処理後のペレットを、乾燥室20に連続して設けられた予熱室30に移行させ、予熱室30内の温度を700℃以上1280℃以下の範囲に保持して、ペレットに対する予熱処理を行った。 Subsequently, the pellets after the drying treatment are transferred to a preheating chamber 30 continuously provided in the drying chamber 20, and the temperature in the preheating chamber 30 is maintained in a range of 700 ° C. or higher and 1280 ° C. or lower, so Heat treatment was performed.

 続いて、予熱処理後のペレットを、回転炉床炉1の内部に移行させて還元処理及び温度保持処理を行った。具体的に、回転炉床炉1としては、炉床が回転移動する領域10を4分割して4つの処理室を備えるものとし、4つの処理室10a~10dをいずれも還元処理を実行する還元室とした。 Subsequently, the pellets after the pre-heat treatment were transferred into the rotary hearth furnace 1 and subjected to reduction treatment and temperature holding treatment. Specifically, as the rotary hearth furnace 1, the region 10 in which the hearth rotates and moves is divided into four, and four processing chambers are provided, and all the four processing chambers 10a to 10d perform reduction processing. The room.

 還元処理を経て得られた還元物については、回転炉床炉1に接続された冷却室に移行させ、窒素を流しながら速やかに室温まで冷却して大気中へ取り出した。なお、還元物の回転炉床炉1からの回収は、冷却室40に還元物を移行させる形態で行い、冷却室40に設置したガイドによって還元物を沿わせるようにして回収した。 The reduced product obtained through the reduction treatment was transferred to a cooling chamber connected to the rotary hearth furnace 1 and quickly cooled to room temperature while flowing nitrogen and taken out into the atmosphere. The reductant was recovered from the rotary hearth furnace 1 in a form in which the reductant was transferred to the cooling chamber 40, and the reductant was recovered along with a guide installed in the cooling chamber 40.

 下記表8~10に、実施例2-1~2-48及び比較例2-1~2-12における、床敷材の材質、床敷材の比表面積、床敷材の平均最大粒子長、還元温度及び還元時間を示す。 In Tables 8 to 10 below, in Examples 2-1 to 2-48 and Comparative Examples 2-1 to 2-12, the material of the flooring material, the specific surface area of the flooring material, the average maximum particle length of the flooring material, The reduction temperature and reduction time are shown.

 なお、床敷材の比表面積は、島津製作所比表面積測定装置(フローソーブIII2305)を用いて測定した。平均最大粒子長は、金属顕微鏡を用いて、無作為に選定し測定した床敷材粒子300個の最大粒子長の平均値より求めた。また、床敷材の体積は、最大粒子長の平均値を求めるのに用いた粒子300個の総重量を測定し、床敷材を構成する材料の密度で割ることにより粒子300個の総体積を求めた。 The specific surface area of the flooring material was measured using a Shimadzu Corporation specific surface area measuring device (Flowsorb III2305). The average maximum particle length was determined from the average value of the maximum particle lengths of 300 floor covering particles randomly selected and measured using a metal microscope. Further, the volume of the flooring material is determined by measuring the total weight of 300 particles used to obtain the average value of the maximum particle length and dividing by the density of the material constituting the flooring material. Asked.

 また、取り出した試料のニッケル品位をICP発光分光分析器(SHIMAZU S-8100)により分析し、ニッケルメタル率とメタル中ニッケル含有率とをそれぞれ算出した。なお、ニッケルメタル率は、下記(4)式により、メタル中ニッケル含有率は下記(5)式により、それぞれ算出した。
 ニッケルメタル化率=還元処理投入ペレット中のメタル化したNiの量/(還元処理投入ペレット中の全てのNi量)×100(%) ・・・(4)
 メタル中ニッケル含有率=還元処理投入ペレット中のメタル化したNiの量/(還元処理投入ペレット中のメタルしたNiとFeの合計量)×100(%)  ・・・(5)
Further, the nickel quality of the sample taken out was analyzed with an ICP emission spectroscopic analyzer (SHIMAZU S-8100), and the nickel metal ratio and the nickel content in the metal were calculated. The nickel metal ratio was calculated by the following formula (4), and the nickel content in the metal was calculated by the following formula (5).
Nickel metalization rate = amount of Ni metalized in the reduction treatment input pellet / (total amount of Ni in the reduction treatment input pellet) × 100 (%) (4)
Nickel content in metal = amount of Ni metalized in the reduction treatment input pellet / (total amount of metal Ni and Fe in the reduction treatment input pellet) × 100 (%) (5)

 さらに、回収した各試料は、湿式処理による粉砕後、磁力選別によってメタルを回収した。そして、ニッケル酸化鉱石の投入量、その中のNi含有割合、及び回収したNi量からNiメタル回収率を算出した。Niメタル回収率は、下記の(6)式により求めた。
 Niメタル回収率={回収したNi量/(ニッケル酸化鉱石の投入量×Ni含有割合)}×100  ・・・(6)
Further, each collected sample was pulverized by wet processing, and then metal was collected by magnetic sorting. Then, the Ni metal recovery rate was calculated from the input amount of nickel oxide ore, the Ni content ratio therein, and the recovered Ni amount. The Ni metal recovery rate was determined by the following equation (6).
Ni metal recovery rate = {recovered Ni amount / (input amount of nickel oxide ore × Ni content ratio)} × 100 (6)

 下記表8~10に、実施例2-1~2-48及び比較例2-1~2-12により得られた試料のニッケルメタル率、メタル中ニッケル含有率及びニッケル回収率を示す。 Tables 8 to 10 below show the nickel metal ratio, the nickel content in the metal, and the nickel recovery rate of the samples obtained in Examples 2-1 to 2-48 and Comparative Examples 2-1 to 2-12.

Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008

Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000009

Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000010

 このように、実施例2-1~2-48においては、所定の床敷材を用いたことにより、均一で安定した還元を行うことができ、その結果Niメタル化率及び回収率が高く、Niについて高品質のフェロニッケルを製造することができた。また、床敷材を連続的に使用することができ、ニッケルを安価に製造することができる。さらに、Ni含有割合メタル成分が多いためにメタルの粗大化が生じやすい。 As described above, in Examples 2-1 to 2-48, by using a predetermined floor covering material, uniform and stable reduction can be performed. As a result, the Ni metalization rate and the recovery rate are high, High quality ferronickel could be produced for Ni. Moreover, a floor covering material can be used continuously and nickel can be manufactured cheaply. Further, since the Ni content ratio metal component is large, the metal tends to be coarsened.

〔実施例3〕
 (混合処理工程)
 原料の酸化鉱石としてのニッケル酸化鉱石と、鉄鉱石と、フラックス成分である珪砂及び石灰石と、バインダーと、炭素質還元剤である石炭とを、適量の水を添加しながら混合機を用いて混合して混合物を得た。なお、炭素質還元剤は、酸化ニッケルと酸化鉄(Fe)とを過不足なくメタルに還元するのに必要な化学当量の合計値を100%としたときに、炭素量で30%に相当する分量で含有させた。
Example 3
(Mixing process)
Mix nickel oxide ore as raw material oxide ore, iron ore, silica sand and limestone as flux components, binder and coal as carbonaceous reducing agent using a mixer while adding appropriate amount of water. To obtain a mixture. The carbonaceous reducing agent is 30% in terms of carbon when the total value of chemical equivalents required for reducing nickel oxide and iron oxide (Fe 2 O 3 ) to metal without excess or deficiency is 100%. In an amount corresponding to.

 そして、混合機によって混合して得られた混合物を、二軸混練機によって混練した。 The mixture obtained by mixing with a mixer was kneaded with a twin-screw kneader.

 (還元投入前処理工程)
 実施例3-1~3-12、実施例3-25~3-36、比較例3-1、比較例3-2、比較例3-5及び比較例3-6については、混練して得られた混合物試料を、パン型造粒機を用いてφ16±1.5mmの球状のペレットに成形した。
(Reduction input pretreatment process)
Examples 3-1 to 3-12, Examples 3-25 to 3-36, Comparative Example 3-1, Comparative Example 3-2, Comparative Example 3-5, and Comparative Example 3-6 were obtained by kneading. The obtained mixture sample was formed into spherical pellets of φ16 ± 1.5 mm using a pan granulator.

 実施例3-13~3-24、実施例3-37~3-48、比較例3-3、比較例3-4、比較例3-7及び比較例3-8については、縦15mm×横15mm×高さ10mmの直方体状となるように混合物を型にはめ込み成形した。 For Examples 3-13 to 3-24, Examples 3-37 to 3-48, Comparative Example 3-3, Comparative Example 3-4, Comparative Example 3-7, and Comparative Example 3-8, 15 mm long × horizontal The mixture was molded into a mold so as to have a rectangular parallelepiped shape of 15 mm × 10 mm in height.

 (還元処理工程)
 次に、図3に例示したような回転炉床炉1を用い、その回転炉床炉1の炉床に、粒子から構成される床敷材を敷き、混合物試料を用いて処理条件を変えて還元処理を行った。回転炉床炉1としては、図3に示すように、領域10の外に、ペレットを乾燥する乾燥室20と、乾燥室20に連続して設けられた予熱室30と、炉内における処理室10a~10dを経て得られた還元物を冷却する冷却室40とが接続されているものを用いた。なお、実施例3においては、処理室10dを冷却室として用いた。
(Reduction treatment process)
Next, using the rotary hearth furnace 1 illustrated in FIG. 3, the flooring material composed of particles is laid on the hearth of the rotary hearth furnace 1, and the processing conditions are changed using the mixture sample. Reduction treatment was performed. As shown in FIG. 3, the rotary hearth furnace 1 includes a drying chamber 20 for drying pellets, a preheating chamber 30 provided continuously to the drying chamber 20, and a processing chamber in the furnace, as shown in FIG. 3. What connected with the cooling chamber 40 which cools the reduced material obtained through 10a-10d was used. In Example 3, the processing chamber 10d was used as a cooling chamber.

 具体的には、ペレット試料を、回転炉床炉1の炉外に接続された乾燥室20に装入し、乾燥処理を施した。乾燥処理は、実質的に酸素を含まない窒素雰囲気中において、ペレット中を固形分が70重量%程度、水分が30重量%程度となるように、250℃~350℃の熱風をペレットに吹き付けることによって行った。下記表11に、乾燥処理後のペレットの固形分組成(炭素を除く)を示す。 Specifically, the pellet sample was placed in the drying chamber 20 connected to the outside of the rotary hearth furnace 1 and dried. In the drying process, hot air of 250 ° C. to 350 ° C. is blown onto the pellets in a nitrogen atmosphere that does not substantially contain oxygen so that the pellets have a solid content of about 70% by weight and water content of about 30% by weight. Went by. Table 11 below shows the solid content composition (excluding carbon) of the pellets after the drying treatment.

Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000011

 続いて、乾燥処理後のペレットを、乾燥室20に連続して設けられた予熱室30に移行させ、予熱室30内の温度を700℃以上1280℃以下の範囲に保持して、ペレットに対する予熱処理を行った。 Subsequently, the pellets after the drying treatment are transferred to a preheating chamber 30 continuously provided in the drying chamber 20, and the temperature in the preheating chamber 30 is maintained in a range of 700 ° C. or higher and 1280 ° C. or lower, so Heat treatment was performed.

 続いて、予熱処理後のペレットを、回転炉床炉1の内部に移行させて還元処理及び温度保持処理を行った。具体的に、回転炉床炉1としては、炉床が回転移動する領域10を4分割して4つの処理室を備えるものとし、4つの処理室10a~10dをいずれも還元処理を実行する還元室とした。 Subsequently, the pellets after the pre-heat treatment were transferred into the rotary hearth furnace 1 and subjected to reduction treatment and temperature holding treatment. Specifically, as the rotary hearth furnace 1, the region 10 in which the hearth rotates and moves is divided into four, and four processing chambers are provided, and all the four processing chambers 10a to 10d perform reduction processing. The room.

 還元処理を経て得られた還元物については、回転炉床炉1に接続された冷却室に移行させ、窒素を流しながら速やかに室温まで冷却して大気中へ取り出した。なお、還元物の回転炉床炉1からの回収は、冷却室40に還元物を移行させる形態で行い、冷却室40に設置したガイドによって還元物を沿わせるようにして回収した。 The reduced product obtained through the reduction treatment was transferred to a cooling chamber connected to the rotary hearth furnace 1 and quickly cooled to room temperature while flowing nitrogen and taken out into the atmosphere. The reductant was recovered from the rotary hearth furnace 1 in a form in which the reductant was transferred to the cooling chamber 40, and the reductant was recovered along with a guide installed in the cooling chamber 40.

 下記表12~14に、実施例3-1~3-48及び比較例3-1~3-12における、床敷材の材質、最大粒子長が50.0μm以下の粒子数の割合、床敷材の平均最大粒子長、還元温度及び還元時間を示す。 In Tables 12 to 14 below, the materials of the flooring material, the ratio of the number of particles having a maximum particle length of 50.0 μm or less, and the flooring in Examples 3-1 to 3-48 and Comparative Examples 3-1 to 3-12 The average maximum particle length, reduction temperature and reduction time of the material are shown.

 なお、床敷材の比表面積は、島津製作所比表面積測定装置(フローソーブIII2305)を用いて測定した。最大粒子長の平均値は、金属顕微鏡を用いて、無作為に選定し測定した床敷材粒子300個の最大粒子長の平均値を求めた。 The specific surface area of the flooring material was measured using a Shimadzu Corporation specific surface area measuring device (Flowsorb III2305). For the average value of the maximum particle length, an average value of the maximum particle lengths of 300 flooring material particles randomly selected and measured using a metal microscope was obtained.

 また、取り出した試料のニッケル品位をICP発光分光分析器(SHIMAZU S-8100)により分析し、ニッケルメタル率とメタル中ニッケル含有率とをそれぞれ算出した。なお、ニッケルメタル率は、下記(4)式により、メタル中ニッケル含有率は下記(5)式により、それぞれ算出した。
 ニッケルメタル化率=還元処理投入ペレット中のメタル化したNiの量/(還元処理投入ペレット中の全てのNi量)×100(%) ・・・(4)
 メタル中ニッケル含有率=還元処理投入ペレット中のメタル化したNiの量/(還元処理投入ペレット中のメタルしたNiとFeの合計量)×100(%)  ・・・(5)
Further, the nickel quality of the sample taken out was analyzed with an ICP emission spectroscopic analyzer (SHIMAZU S-8100), and the nickel metal ratio and the nickel content in the metal were calculated. The nickel metal ratio was calculated by the following formula (4), and the nickel content in the metal was calculated by the following formula (5).
Nickel metalization rate = amount of Ni metalized in the reduction treatment input pellet / (total amount of Ni in the reduction treatment input pellet) × 100 (%) (4)
Nickel content in metal = amount of Ni metalized in the reduction treatment input pellet / (total amount of metal Ni and Fe in the reduction treatment input pellet) × 100 (%) (5)

 さらに、回収した各試料は、湿式処理による粉砕後、磁力選別によってメタルを回収した。そして、ニッケル酸化鉱石の投入量、その中のNi含有割合、及び回収したNi量からNiメタル回収率を算出した。Niメタル回収率は、下記の(6)式により求めた。
 Niメタル回収率={回収したNi量/(ニッケル酸化鉱石の投入量×Ni含有割合)}×100  ・・・(6)
Further, each collected sample was pulverized by wet processing, and then metal was collected by magnetic sorting. Then, the Ni metal recovery rate was calculated from the input amount of nickel oxide ore, the Ni content ratio therein, and the recovered Ni amount. The Ni metal recovery rate was determined by the following equation (6).
Ni metal recovery rate = {recovered Ni amount / (input amount of nickel oxide ore × Ni content ratio)} × 100 (6)

 下記表12~14に、実施例3-1~3-48及び比較例3-1~3-12により得られた試料のニッケルメタル率、メタル中ニッケル含有率及びニッケル回収率を示す。 Tables 12 to 14 below show the nickel metal ratio, the nickel content in the metal, and the nickel recovery rate of the samples obtained in Examples 3-1 to 3-48 and Comparative Examples 3-1 to 3-12.

Figure JPOXMLDOC01-appb-T000012
Figure JPOXMLDOC01-appb-T000012

Figure JPOXMLDOC01-appb-T000013
Figure JPOXMLDOC01-appb-T000013

Figure JPOXMLDOC01-appb-T000014
Figure JPOXMLDOC01-appb-T000014

 このように、実施例3-1~3-48においては、所定の床敷材を用いたことにより、均一で安定した還元を行うことができ、その結果Niメタル化率及び回収率が高く、Niについて高品質のフェロニッケルを製造することができた。また、床敷材を連続的に使用することができ、ニッケルを安価に製造することができる。さらに、Ni含有割合メタル成分が多いためにメタルの粗大化が生じやすい。 As described above, in Examples 3-1 to 3-48, by using a predetermined floor covering material, uniform and stable reduction can be performed. As a result, the Ni metalization rate and the recovery rate are high, High quality ferronickel could be produced for Ni. Moreover, a floor covering material can be used continuously and nickel can be manufactured cheaply. Further, since the Ni content ratio metal component is large, the metal tends to be coarsened.

〔実施例4〕
 (混合処理工程)
 原料の酸化鉱石としてのニッケル酸化鉱石と、鉄鉱石と、フラックス成分である珪砂及び石灰石と、バインダーと、炭素質還元剤である石炭とを、適量の水を添加しながら混合機を用いて混合して混合物を得た。なお、炭素質還元剤は、酸化ニッケルと酸化鉄(Fe)とを過不足なくメタルに還元するのに必要な化学当量の合計値を100%としたときに、炭素量で30%に相当する分量で含有させた。
Example 4
(Mixing process)
Mix nickel oxide ore as raw material oxide ore, iron ore, silica sand and limestone as flux components, binder and coal as carbonaceous reducing agent using a mixer while adding appropriate amount of water. To obtain a mixture. The carbonaceous reducing agent is 30% in terms of carbon when the total value of chemical equivalents required for reducing nickel oxide and iron oxide (Fe 2 O 3 ) to metal without excess or deficiency is 100%. In an amount corresponding to.

 そして、混合機によって混合して得られた混合物を、二軸混練機によって混練した。 The mixture obtained by mixing with a mixer was kneaded with a twin-screw kneader.

 (還元投入前処理工程)
 実施例4-1~4-12、実施例4-25~4-36、比較例4-1、比較例4-2、比較例4-5及び比較例4-6については、混練して得られた混合物試料を、パン型造粒機を用いてφ15±1.5mmの球状のペレットに成形した。
(Reduction input pretreatment process)
Examples 4-1 to 4-12, Examples 4-25 to 4-36, Comparative Example 4-1, Comparative Example 4-2, Comparative Example 4-5 and Comparative Example 4-6 were obtained by kneading. The obtained mixture sample was formed into spherical pellets with a diameter of 15 ± 1.5 mm using a bread granulator.

 実施例4-13~4-24、実施例4-37~4-48、比較例4-3、比較例4-4、比較例4-7及び比較例4-8については、縦15mm×横15mm×高さ10mmの直方体状となるように混合物試料を型にはめ込み成形した。 For Examples 4-13 to 4-24, Examples 4-37 to 4-48, Comparative Example 4-3, Comparative Example 4-4, Comparative Example 4-7, and Comparative Example 4-8, 15 mm long × horizontal The mixture sample was molded into a mold so as to have a rectangular parallelepiped shape of 15 mm × 10 mm in height.

 (還元処理工程)
 次に、図3に例示したような回転炉床炉1を用いて、混合物試料を用いて処理条件を変えて還元処理を行った。回転炉床炉1としては、図3に示すように、領域10の外に、ペレットを乾燥する乾燥室20と、乾燥室20に連続して設けられた予熱室30と、炉内における処理室10a~10dを経て得られた還元物を冷却する冷却室40とが接続されているものを用いた。なお、実施例4においては、処理室10dを冷却室として用いた。
(Reduction treatment process)
Next, using the rotary hearth furnace 1 illustrated in FIG. 3, reduction treatment was performed by changing the treatment conditions using the mixture sample. As shown in FIG. 3, the rotary hearth furnace 1 includes a drying chamber 20 for drying pellets, a preheating chamber 30 provided continuously to the drying chamber 20, and a processing chamber in the furnace, as shown in FIG. 3. What connected with the cooling chamber 40 which cools the reduced material obtained through 10a-10d was used. In Example 4, the processing chamber 10d was used as a cooling chamber.

 具体的には、ペレット試料を、回転炉床炉1の炉外に接続された乾燥室20に装入し、乾燥処理を施した。乾燥処理は、実質的に酸素を含まない窒素雰囲気中において、ペレット中を固形分が70重量%程度、水分が30重量%程度となるように、250℃~350℃の熱風をペレットに吹き付けることによって行った。下記表15に、乾燥処理後のペレットの固形分組成(炭素を除く)を示す。 Specifically, the pellet sample was placed in the drying chamber 20 connected to the outside of the rotary hearth furnace 1 and dried. In the drying process, hot air of 250 ° C. to 350 ° C. is blown onto the pellets in a nitrogen atmosphere that does not substantially contain oxygen so that the pellets have a solid content of about 70% by weight and water content of about 30% by weight. Went by. Table 15 below shows the solid content composition (excluding carbon) of the pellets after the drying treatment.

Figure JPOXMLDOC01-appb-T000015
Figure JPOXMLDOC01-appb-T000015

 続いて、乾燥処理後のペレットを、乾燥室20に連続して設けられた予熱室30に移行させ、予熱室30内の温度を700℃以上1280℃以下の範囲に保持して、ペレットに対する予熱処理を行った。 Subsequently, the pellets after the drying treatment are transferred to a preheating chamber 30 continuously provided in the drying chamber 20, and the temperature in the preheating chamber 30 is maintained in a range of 700 ° C. or higher and 1280 ° C. or lower, so Heat treatment was performed.

 続いて、予熱処理後のペレットを、回転炉床炉1の内部に移行させて還元処理及び温度保持処理を行った。具体的に、回転炉床炉1としては、炉床が回転移動する領域10を4分割して4つの処理室を備えるものとし、4つの処理室10a~10dをいずれも還元処理を実行する還元室とした。 Subsequently, the pellets after the pre-heat treatment were transferred into the rotary hearth furnace 1 and subjected to reduction treatment and temperature holding treatment. Specifically, as the rotary hearth furnace 1, the region 10 in which the hearth rotates and moves is divided into four, and four processing chambers are provided, and all the four processing chambers 10a to 10d perform reduction processing. The room.

 還元処理を経て得られた還元物については、回転炉床炉1に接続された冷却室に移行させ、窒素を流しながら速やかに室温まで冷却して大気中へ取り出した。なお、還元物の回転炉床炉1からの回収は、冷却室40に還元物を移行させる形態で行い、冷却室40に設置したガイドによって還元物を沿わせるようにして回収した。 The reduced product obtained through the reduction treatment was transferred to a cooling chamber connected to the rotary hearth furnace 1 and quickly cooled to room temperature while flowing nitrogen and taken out into the atmosphere. The reductant was recovered from the rotary hearth furnace 1 in a form in which the reductant was transferred to the cooling chamber 40, and the reductant was recovered along with a guide installed in the cooling chamber 40.

 下記表16~18に、実施例4-1~4-48及び比較例4-1~4-12における、床敷材の材質、床敷材の形状、炉床に対する混合物の配置面積率、還元温度及び還元時間を示す。 In Tables 16 to 18 below, in Examples 4-1 to 4-48 and Comparative Examples 4-1 to 4-12, the material of the floor covering material, the shape of the floor covering material, the arrangement area ratio of the mixture with respect to the hearth, and the reduction Temperature and reduction time are indicated.

 また、取り出した試料のニッケル品位をICP発光分光分析器(SHIMAZU S-8100)により分析し、ニッケルメタル率とメタル中ニッケル含有率とをそれぞれ算出した。なお、ニッケルメタル率は、下記(4)式により、メタル中ニッケル含有率は下記(5)式により、それぞれ算出した。
 ニッケルメタル化率=還元処理投入ペレット中のメタル化したNiの量/(還元処理投入ペレット中の全てのNi量)×100(%) ・・・(4)
 メタル中ニッケル含有率=還元処理投入ペレット中のメタル化したNiの量/(還元処理投入ペレット中のメタルしたNiとFeの合計量)×100(%)  ・・・(5)
Further, the nickel quality of the sample taken out was analyzed with an ICP emission spectroscopic analyzer (SHIMAZU S-8100), and the nickel metal ratio and the nickel content in the metal were calculated. The nickel metal ratio was calculated by the following formula (4), and the nickel content in the metal was calculated by the following formula (5).
Nickel metalization rate = amount of Ni metalized in the reduction treatment input pellet / (total amount of Ni in the reduction treatment input pellet) × 100 (%) (4)
Nickel content in metal = amount of Ni metalized in the reduction treatment input pellet / (total amount of metal Ni and Fe in the reduction treatment input pellet) × 100 (%) (5)

 さらに、回収した各試料は、湿式処理による粉砕後、磁力選別によってメタルを回収した。そして、ニッケル酸化鉱石の投入量、その中のNi含有割合、及び回収したNi量からNiメタル回収率を算出した。Niメタル回収率は、下記の(6)式により求めた。
 Niメタル回収率={回収したNi量/(ニッケル酸化鉱石の投入量×Ni含有割合)}×100  ・・・(6)
Further, each collected sample was pulverized by wet processing, and then metal was collected by magnetic sorting. Then, the Ni metal recovery rate was calculated from the input amount of nickel oxide ore, the Ni content ratio therein, and the recovered Ni amount. The Ni metal recovery rate was determined by the following equation (6).
Ni metal recovery rate = {recovered Ni amount / (input amount of nickel oxide ore × Ni content ratio)} × 100 (6)

 下記表16~18に、実施例4-1~4-48及び比較例4-1~4-8により得られた試料のニッケルメタル率、メタル中ニッケル含有率及びニッケル回収率を示す。 Tables 16 to 18 below show the nickel metal ratio, the nickel content in the metal, and the nickel recovery rate of the samples obtained in Examples 4-1 to 4-48 and Comparative Examples 4-1 to 4-8.

Figure JPOXMLDOC01-appb-T000016
Figure JPOXMLDOC01-appb-T000016

Figure JPOXMLDOC01-appb-T000017
Figure JPOXMLDOC01-appb-T000017

Figure JPOXMLDOC01-appb-T000018
Figure JPOXMLDOC01-appb-T000018

 このように、実施例4-1~4-48においては、炉床に対し特定の割合で混合物を配置したことにより、均一で安定した還元を行うことができ、その結果Niメタル化率及び回収率が高く、Niについて高品質のフェロニッケルを製造することができた。また、床敷材を連続的に使用することができ、ニッケルを安価に製造することができる。さらに、Ni含有割合メタル成分が多いためにメタルの粗大化が生じやすい。 As described above, in Examples 4-1 to 4-48, the mixture was arranged at a specific ratio with respect to the hearth, so that uniform and stable reduction could be performed. As a result, the Ni metalization rate and the recovery were achieved. The rate was high and it was possible to produce high quality ferronickel for Ni. Moreover, a floor covering material can be used continuously and nickel can be manufactured cheaply. Further, since the Ni content ratio metal component is large, the metal tends to be coarsened.

 1  回転炉床炉
 10  領域
 10a,10b,10c,10d  処理室(還元室、温度保持室、冷却室)
 20  乾燥室
 30  予熱室
 40  冷却室
 51  混合物(球状)
 52  床敷材
 61  混合物(立方体状)
 62  床敷材
 
 
1 rotary hearth furnace 10 region 10a, 10b, 10c, 10d processing chamber (reduction chamber, temperature holding chamber, cooling chamber)
20 Drying room 30 Preheating room 40 Cooling room 51 Mixture (spherical)
52 Flooring material 61 Mixture (cubic)
62 Flooring material

Claims (11)

 還元炉内で、金属酸化物と炭素質還元剤とを混合して得られた混合物を還元する金属酸化物の製錬方法であって、
 アルミナ、アルミナセメント、マグネシア、マグネシアセメント、ジルコニア、ジルコニアセメント及びムライトから選択される1種以上の材料から構成される床敷材上で、前記混合物を加熱し還元する
 金属酸化物の製錬方法。
A metal oxide smelting method for reducing a mixture obtained by mixing a metal oxide and a carbonaceous reducing agent in a reduction furnace,
A metal oxide smelting method in which the mixture is heated and reduced on a floor covering composed of one or more materials selected from alumina, alumina cement, magnesia, magnesia cement, zirconia, zirconia cement and mullite.
 前記床敷材は、前記材料の粒子(床敷材粒子)から構成され、
 下記式(1)及び(2)より求められる平均床敷材体積率が3%以上85%以下である
 請求項1に記載の金属酸化物の製錬方法。
 平均床敷材体積率
 =床敷材粒子300個の床敷材体積率の総和/300  ・・・(1)
 床敷材体積率
 =(床敷材粒子の体積/床敷材粒子の最大粒子長を直径とする球の体積)×100  ・・・(2)
The flooring material is composed of particles of the material (flooring material particles),
The method for smelting a metal oxide according to claim 1, wherein an average flooring material volume ratio obtained from the following formulas (1) and (2) is 3% or more and 85% or less.
Average floor covering volume ratio = total floor covering volume ratio of 300 floor covering particles / 300 (1)
Floor covering volume ratio = (volume of floor covering particles / volume of sphere having diameter of maximum particle length of floor covering particles) × 100 (2)
 前記床敷材は、前記材料の粒子(床敷材粒子)から構成され、
 下記式(3)より求められる平均最大粒子長が10μm以上6000μm以下である
 請求項1又は2に記載の金属酸化物の製錬方法。
 平均最大粒子長
 =床敷材粒子300個の最大粒子長の総和/300  ・・・(3)
The flooring material is composed of particles of the material (flooring material particles),
The average maximum particle length calculated | required from following formula (3) is 10 micrometers or more and 6000 micrometers or less. The smelting method of the metal oxide of Claim 1 or 2.
Average maximum particle length = sum of maximum particle lengths of 300 flooring particles / 300 (3)
 還元炉内で、金属酸化物と炭素質還元剤とを混合して得られた混合物を還元する金属酸化物の製錬方法であって、
 比表面積が0.001μm-1以上3.0μm-1以下であり、且つ平均最大粒子長が15.0μm以上2000μm以下である粒子(床敷材粒子)から構成される床敷材上で、前記混合物を加熱し還元する
 金属酸化物の製錬方法。
A metal oxide smelting method for reducing a mixture obtained by mixing a metal oxide and a carbonaceous reducing agent in a reduction furnace,
The specific surface area is at 0.001 [mu] m -1 or more 3.0 [mu] m -1 or less, and an average maximum particle length is bedding material onto comprised particles less 2000μm or more 15.0 .mu.m (bedding material particles), the A method for smelting a metal oxide, wherein the mixture is heated and reduced.
 前記床敷材粒子は、アルミナ、アルミナセメント、マグネシア、マグネシアセメント、ジルコニア、ジルコニアセメント及びムライトから選択される1種以上の材料から構成される
 請求項4に記載の金属酸化物の製錬方法。
The metal oxide smelting method according to claim 4, wherein the flooring material particles are composed of one or more materials selected from alumina, alumina cement, magnesia, magnesia cement, zirconia, zirconia cement, and mullite.
 還元炉内で、金属酸化物と炭素質還元剤とを混合して得られた混合物を還元する金属酸化物の製錬方法であって、
 前記還元炉の炉床上に床敷材を敷き、
 前記床敷材は粒子(床敷材粒子)から構成され、該床敷材に含まれる最大粒子長50.0μm以下の床敷材粒子の数が、該床敷材に含まれる総床敷材粒子の数に対し1%以上40%以下であり、
 前記床敷材粒子は、下記式(3)により求められる平均最大粒子長が40.0μm以上1050μm以下である
 金属酸化物の製錬方法。
 平均最大粒子長
 =床敷材粒子300個の最大粒子長の総和/300  ・・・(3)
A metal oxide smelting method for reducing a mixture obtained by mixing a metal oxide and a carbonaceous reducing agent in a reduction furnace,
Laying flooring material on the hearth of the reduction furnace,
The flooring material is composed of particles (flooring material particles), and the total number of flooring material particles having a maximum particle length of 50.0 μm or less contained in the flooring material is included in the flooring material. 1% to 40% of the number of particles,
The flooring material particles have a mean maximum particle length of 40.0 μm or more and 1050 μm or less determined by the following formula (3).
Average maximum particle length = sum of maximum particle lengths of 300 flooring particles / 300 (3)
 還元炉内で、金属酸化物と炭素質還元剤とを混合して得られた混合物を還元する金属酸化物の製錬方法であって、
 前記還元炉の炉床上に床敷材を敷き、
 前記床敷材上に、前記炉床を平面視したときに該炉床の面積の50%以下となるように前記混合物を配置して加熱し還元する
 金属酸化物の製錬方法。
A metal oxide smelting method for reducing a mixture obtained by mixing a metal oxide and a carbonaceous reducing agent in a reduction furnace,
Laying flooring material on the hearth of the reduction furnace,
A method for smelting metal oxide, wherein the mixture is placed on the floor covering material so as to be 50% or less of the area of the hearth when viewed in plan, and heated and reduced.
 前記混合物は、球状、立方体状又は直方体状のいずれかの形状を有する
 請求項7に記載の金属酸化物の製錬方法。
The metal oxide smelting method according to claim 7, wherein the mixture has a spherical shape, a cubic shape, or a rectangular parallelepiped shape.
 還元温度が、1200℃以上1450℃以下である
 請求項1乃至8のいずれか1項に記載の金属酸化物の製錬方法。
The method for smelting a metal oxide according to any one of claims 1 to 8, wherein the reduction temperature is from 1200C to 1450C.
 前記金属酸化物は、ニッケル酸化鉱石である
 請求項1乃至9のいずれか1項に記載の金属酸化物の製錬方法。
The metal oxide smelting method according to any one of claims 1 to 9, wherein the metal oxide is nickel oxide ore.
 前記還元物は、フェロニッケルを含有する
 請求項1乃至10のいずれか1項に記載の金属酸化物の製錬方法。
The metal oxide smelting method according to any one of claims 1 to 10, wherein the reduced product contains ferronickel.
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