WO2020059630A1 - 酸化鉱石の製錬方法 - Google Patents
酸化鉱石の製錬方法 Download PDFInfo
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- WO2020059630A1 WO2020059630A1 PCT/JP2019/035891 JP2019035891W WO2020059630A1 WO 2020059630 A1 WO2020059630 A1 WO 2020059630A1 JP 2019035891 W JP2019035891 W JP 2019035891W WO 2020059630 A1 WO2020059630 A1 WO 2020059630A1
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- reduction
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/023—Alloys based on nickel
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/24—Binding; Briquetting ; Granulating
- C22B1/242—Binding; Briquetting ; Granulating with binders
- C22B1/243—Binding; Briquetting ; Granulating with binders inorganic
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/02—Obtaining nickel or cobalt by dry processes
- C22B23/023—Obtaining nickel or cobalt by dry processes with formation of ferro-nickel or ferro-cobalt
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
- C22B5/10—Dry methods smelting of sulfides or formation of mattes by solid carbonaceous reducing agents
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/04—Making ferrous alloys by melting
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/10—Reduction of greenhouse gas [GHG] emissions
- Y02P10/134—Reduction of greenhouse gas [GHG] emissions by avoiding CO2, e.g. using hydrogen
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Definitions
- the present invention relates to a method for dry smelting of an oxide ore, and more particularly, to a smelting method for producing a metal as a reductant by reducing an oxide ore such as a nickel oxide ore as a raw material with a carbonaceous reducing agent. About the method.
- limonite or saprolite As a method for smelting nickel oxide ore called limonite or saprolite, which is a kind of oxide ore, a dry smelting method using a smelting furnace to produce nickel matte, and iron and nickel using a rotary kiln or moving hearth furnace
- a dry smelting method for producing ferronickel which is an alloy of the present invention
- the nickel oxide ore as a raw material is crushed to an appropriate size in order to advance the reaction. Agglomeration processing is performed as preprocessing.
- the nickel oxide ore when the nickel oxide ore is agglomerated, that is, when the powdered or fine ore is agglomerated, the nickel oxide ore is mixed with other components, for example, a reducing agent such as a binder or coke. The mixture is further adjusted for water content, and then charged into a lump manufacturing machine, for example, lump having a side or a diameter of about 10 mm to 30 mm (refers to a pellet, briquette, etc., hereinafter simply referred to as “pellet”). ).
- a lump manufacturing machine for example, lump having a side or a diameter of about 10 mm to 30 mm (refers to a pellet, briquette, etc., hereinafter simply referred to as “pellet”).
- the pellets obtained by agglomeration need to have a certain degree of air permeability in order to "blow off" the contained water. Further, if the reduction does not proceed uniformly in the pellets in the subsequent reduction treatment, the composition of the obtained reduced product becomes non-uniform, which causes inconveniences such as dispersion or uneven distribution of the metal. Therefore, it is important to uniformly mix the mixture when preparing pellets and to maintain the temperature as uniform as possible when reducing the obtained pellets.
- ferronickel metal (ferronickel) generated by the reduction treatment. If the produced ferronickel has a fine size of, for example, several tens ⁇ m to several hundreds ⁇ m or less, it becomes difficult to separate it from the slag produced at the same time, and the recovery rate (yield) as ferronickel is greatly reduced. I will. Therefore, a treatment for coarsening the reduced ferronickel is required.
- Patent Literature 1 discloses a method of manufacturing a granular metal by heating an agglomerate containing a metal oxide and a carbonaceous reducing agent to reduce and melt a metal oxide contained in the agglomerate to produce a granular metal.
- a technique for the purpose of proposing a technique for further improving productivity Specifically, an agglomerate containing a metal oxide and a carbonaceous reducing agent is supplied onto a hearth of a moving bed type reduction melting furnace and heated to reduce and melt the metal oxide.
- the furnace temperature in the first half of the furnace for solid-reducing iron oxide in agglomerates is 1300 to 1450 ° C.
- the furnace temperature in the latter half of the furnace where the reduced iron in the agglomerate is carburized, melted and agglomerated is 1400 to 1550 ° C.
- the distance between the agglomerates spread on the hearth is 0
- the relative density of the projected area ratio of the agglomerate laid on the hearth to the hearth is defined as the bed density, relative to the maximum projected area ratio of the agglomerate to the hearth
- the average diameter is 19.5 mm.
- Patent Document 1 also discloses that productivity can be improved by controlling the density of the agglomerates together with the average diameter of the agglomerates to improve the productivity of granular metallic iron.
- Patent Document 1 is a technology relating to the reaction on the outer surface of the clumps, but the most important factor for the reduction reaction is, of course, the state in the agglomerate where the reduction reaction occurs. No. That is, it is considered that by controlling the reduction reaction inside the agglomerate, the reaction efficiency and the uniform reduction reaction are realized, and as a result, a high-quality metal can be produced.
- the diameter of the agglomerate is limited to a predetermined range as in the technique described in Patent Document 1, a decrease in the yield when producing the agglomerate is inevitable, and as a result, the cost is reduced. There is concern that it will be up. If the bed density of the agglomerate is in the range of 0.5 to 0.8, the packing is not finely packed, and it is difficult to laminate the agglomerate.
- the present invention has been proposed in view of such circumstances, and an object of the present invention is to provide a method for smelting an oxide ore capable of efficiently producing high-quality metal.
- the present inventor has conducted extensive studies, and as described above, using a reduction furnace having a burner, reducing the mixture containing the oxide ore and the carbonaceous reducing agent to a molten state by heating the mixture with the burner, thereby reducing the temperature.
- the inventors have found that the problem can be solved, and have completed the present invention.
- a first invention of the present invention is a method for refining a mixture of an oxide ore and a carbonaceous reducing agent to produce a metal as a reductant, the method for smelting an oxide ore, comprising: And reducing the oxide ore by heating the mixture with a burner to obtain metal and slag in a molten state.
- the oxide ore is a nickel oxide ore
- ferronickel is produced by reducing a mixture containing the nickel oxide ore. It is a smelting method.
- the temperature of the metal and slag obtained in the reduction furnace is 1300 ° C or more and 1700 ° C or less, respectively.
- the air-fuel ratio of the burner is controlled to fall within a range of 0.8 or more and 1.1 or less. This is a method for smelting oxide ores by heating the mixture.
- the sixth invention of the present invention further comprising a drying step of drying the mixture, wherein the drying step uses a gas generated in the reduction furnace. And drying the mixture, and subjecting the dried mixture to the treatment in the reduction step.
- the drying step in the drying step, the mixture is dried in a drying facility directly connected to the reduction furnace, and the drying step is performed in the drying facility.
- a method for smelting oxide ore in which a gas generated in the reduction furnace by the reduction treatment is introduced directly from the reduction furnace.
- An eighth invention according to the present invention is a smelting reduction furnace for smelting and reducing a mixture of an oxide ore and a carbonaceous reducing agent, the smelting reduction furnace having a drying section for drying the mixture, and a burner.
- a reduction treatment unit for reducing the oxide ore by heating the mixture after drying in the treatment unit with the burner to obtain a metal and a slag in a molten state, and the drying treatment unit in a height direction. are provided in the same space located above and below the reduction processing unit, respectively, and in the drying processing unit, the mixture is dried by a gas generated in the reduction processing unit located below. , A smelting reduction furnace.
- the present invention provides an oxide ore for producing a metal as a reduced product by reducing a mixture obtained by mixing an oxide ore such as a nickel oxide ore as a raw material and mixing the oxide ore with a carbonaceous reducing agent. It is a refining method. For example, when nickel oxide ore is used as a raw material ore, ferronickel metal, which is an alloy of nickel and iron, is produced as a reductant.
- a mixture of an oxide ore and a carbonaceous reducing agent is charged into a reduction furnace (burner furnace) having a burner, and the mixture is heated by the burner. And reducing the oxide ore to obtain molten metal and slag.
- metal can be generated with higher productivity in a shorter processing time than before and at a lower cost.
- the metal and slag generated in a molten state are separated (specific gravity separation) by a specific gravity difference in the reduction furnace. Thereby, only the metal can be efficiently recovered in a short time and at low cost.
- Nickel oxide ore smelting method As a specific embodiment of the present invention (hereinafter, referred to as “the present embodiment”), nickel oxide ore is used as a raw material ore, and nickel (nickel oxide) and iron (iron oxide) contained in the nickel oxide ore are used. ) To produce a metal of an iron-nickel alloy (ferronickel), and further, a smelting method for producing ferronickel by separating the metal will be described as an example.
- FIG. 1 is a process chart showing a flow of a method for smelting nickel oxide ore.
- the smelting method of nickel oxide ore according to the present embodiment includes a mixing step S1 of mixing a raw material containing nickel oxide ore, and drying the obtained mixture.
- a drying step S2 a reduction step S3 of heating the dried mixture to a predetermined reduction temperature to reduce the mixture, and a collection step S4 of separating the obtained reduced product metal and slag to collect the metal.
- the mixing step S1 is a step of mixing raw material powders containing nickel oxide ore to obtain a mixture. Specifically, in the mixing step S1, nickel oxide ore, which is a raw material ore, and a carbonaceous reducing agent are mixed, and as an optional additive, for example, iron ore, a flux component, a binder, or the like having a particle size of 0%. A powder of about 1 mm to 0.8 mm is mixed to obtain a mixture.
- a predetermined amount of water can be added.
- the mixing process can be performed using a known mixer or the like.
- the respective raw material powders may be mixed and kneading may be performed to improve the mixing property.
- kneading By performing the kneading, a shearing force is applied to the mixture obtained by mixing the raw material powders, and the aggregation of the raw material ore, the carbon reducing agent, and the like can be released, and the mixture between the particles can be more uniformly mixed and the voids between the respective particles can be reduced.
- the kneading can be performed using a twin-screw kneader or the like.
- the nickel oxide ore which is a raw material ore, is not particularly limited, but limonite ore, saprolite ore, or the like can be used.
- the nickel oxide ore contains nickel oxide (NiO) and iron oxide (Fe 2 O 3 ) as constituent components.
- nickel oxide ore When using nickel oxide ore, it may be classified, crushed, or the like into a predetermined size.
- the particle size can be adjusted to a certain extent, and by eliminating large-sized ore by grinding, etc., the mixing property with the carbonaceous reducing agent etc. is improved, Uniformity can be improved.
- the carbonaceous reducing agent is not particularly limited, and examples thereof include coal powder and coke powder.
- the carbonaceous reducing agent has the same particle size as the nickel oxide ore, which is the raw material ore described above. Thereby, the mixing property with the nickel oxide ore can be enhanced, and the uniformity at the time of the reduction treatment can be improved.
- the mixing amount of the carbonaceous reducing agent is 80% by mass or less when the amount of the carbonaceous reducing agent necessary to reduce nickel oxide and iron oxide constituting the nickel oxide ore without excess or shortage is 100% by mass. , And more preferably 60% by mass or less.
- the mixing amount of the carbonaceous reducing agent is not particularly limited, but is preferably 15% by mass or more based on 100% by mass of the total chemical equivalent, and 20% by mass or more. Is more preferable.
- the amount of the carbonaceous reducing agent required to reduce nickel oxide and iron oxide without excess and deficiency is defined as the chemical equivalent required to reduce the entire amount of nickel oxide to nickel metal, and the amount of iron oxide converted to iron metal.
- total value of the chemical equivalents To the total value of the chemical equivalents necessary for the reduction (hereinafter, also referred to as the "total value of the chemical equivalents").
- the iron ore as an optional additive is not particularly limited.
- iron ore having an iron grade of about 50% by mass or more, hematite obtained by hydrometallurgy of nickel oxide ore, or the like can be used.
- binder examples include bentonite, polysaccharide, resin, water glass, dehydrated cake and the like.
- the flux component include calcium oxide, calcium hydroxide, calcium carbonate, and silicon dioxide.
- Table 1 shows an example of the composition (% by weight) of some raw material powders mixed in the mixing step S1.
- the composition of the raw material powder is not limited to this.
- the drying step S2 is a step of drying the obtained mixture.
- the mixture obtained through the above-described mixing step S1 may be directly charged into a reduction furnace described below and subjected to a reduction treatment (reduction step S3). May be dried.
- the treatment is performed in the drying step S2 as described above, the dried mixture is charged into a reduction furnace, and then subjected to the processing in the reduction step S3.
- the mixture can be uniformly subjected to the reduction treatment, and the mixture can be surely heated to a melting temperature or higher to be reduced.
- the drying temperature is not particularly limited, but is preferably in the range of 150 ° C to 400 ° C.
- the mixture can be efficiently dried while suppressing the progress of the reaction of the mixture in the treatment. Further, even in the case where the mixture is formed into a predetermined shape and subjected to the reduction treatment, by drying the mixture in the above temperature range, it is possible to prevent the molded article from being rapidly heated and ruptured by the reduction treatment. Can be.
- the drying method is not particularly limited. For example, a method in which the mixture is charged into a drying facility whose inside is adjusted to a predetermined drying temperature and dried by holding the mixture for a predetermined time, a method in which hot air at a predetermined drying temperature is sprayed on the mixture, and the like. Can be mentioned.
- drying may be performed using exhaust gas generated in a reduction furnace that performs heat reduction. Since the exhaust gas generated after the reduction treatment has a very high temperature, it is suitable for drying a mixture containing nickel oxide ore. Further, since the temperature is high, the drying process can be performed with a reduced gas flow rate, thereby suppressing the dust generation rate in the drying process.
- Table 2 shows an example of the composition (parts by weight) in the solid content of the mixture after the drying treatment.
- the composition of the mixture is not limited to this.
- the drying process may be performed simultaneously with the mixing in the mixing process S1 described above.
- the drying process S2 Can also be omitted.
- mixing may be performed after drying, and a process may be appropriately selected according to properties of the ore, the carbonaceous reducing agent, and the like.
- the reduction step S3 is a step of charging the mixture into a reduction furnace and reducing the mixture to generate metal and slag.
- a reduction furnace having a burner hereinafter, also referred to as a “burner furnace” is used to reduce the oxide ore by heating the mixture with the burner. .
- the mixture is melted with the progress of the reduction reaction, and metal and slag in a molten state are generated.
- the reduction reaction of the nickel oxide ore gradually progresses with the heating of the mixture charged in the furnace by the burner, so that the mixture is not melted.
- a reduction reaction occurs also in the solid state.
- the mixture gradually changed from a solid state to a liquid state, that is, a molten state by the burner heating, with the progress of the reduction reaction on the nickel oxide ore, and finally produced by a heat reduction treatment by the burner.
- a molten metal and slag are obtained.
- the mixture can only be brought into a semi-molten state, and this requires a long time for metal grains to grow, resulting in an increase in cost. Further, when the semi-molten matter adheres to the kiln and grows, the operation for maintenance must be stopped, and there is a problem that the operation efficiency is significantly reduced.
- the mixture containing oxide ore is reduced by heating with a burner using a burner furnace, so that the mixture can be effectively reduced in a short processing time. Then, nickel can be reduced at a rate of approximately 100% by controlling the atmosphere in the furnace, which allows a sufficient operation, and the reduction rate of iron can be controlled. Thereby, high quality ferronickel can be manufactured at low cost and with high productivity.
- the ore reduction ratio can be controlled by the mixture ratio of the carbonaceous reducing agent in the mixture.
- compositional variation due to oxidation of the generated metal is less likely to occur.
- the mixture becomes a molten state as the reduction reaction progresses, and finally the molten metal and slag are generated.
- the molten metal and slag are generated.
- the molten metal molten metal
- the molten metal is deposited under the slag due to the difference in specific gravity, even if the oxygen partial pressure or the CO partial pressure fluctuates in the furnace atmosphere, the molten metal remains on the furnace bottom under the slag. The effect on the composition of the accumulated metal can be suppressed.
- the treatment can be performed at a much lower cost than in the heating using electricity or the like, and the economic efficiency can be improved.
- a burner furnace for example, LPG gas, LNG gas, coal, coke, pulverized coal, etc. are used as fuels, but the cost of these fuels is very low, and the cost of equipment and maintenance is also low. Compared to an electric furnace or the like, the cost can be significantly reduced.
- FIG. 2 is a diagram (cross-sectional view) schematically showing a configuration example of a reduction furnace having a burner.
- the reduction furnace 10 includes a processing unit 11 that heats the mixture M to perform a reduction process, a charging port 12 that charges the mixture M into the processing unit 11, and a metal obtained by the reduction process. And a discharge port 13 for discharging.
- the inner wall and the hearth of the processing unit 11 are preferably protected by slag coating. Thereby, damage to the furnace can be prevented, continuous operation can be performed for a long period of time, and equipment costs and maintenance costs can be reduced.
- a burner 14 is provided on an upper portion thereof.
- the mixture M charged from the charging port 12 is heated by the burner 14, and a reduction reaction for reducing nickel oxide ore is caused by the carbonaceous reducing agent contained in the mixture M.
- a reduction reaction is caused by heating by the burner 14, and the mixture is brought into a molten state as the reduction reaction proceeds. That is, the reduction furnace 10 is a smelting reduction furnace.
- a metal and slag in a molten state are generated by such a reduction reaction, and a reduced product in which the slag and the metal are separated into an upper layer and a lower layer, respectively, is obtained due to a difference in specific gravity.
- the molten metal separated by the specific gravity difference is discharged.
- the discharge port 13 is provided at a position where a metal (metal layer) constituting a lower layer of the reduced product exists, and can selectively discharge and recover the metal separated due to a difference in specific gravity.
- a slag discharge port can be provided above the discharge port 13, and the slag constituting the upper layer separated by the specific gravity difference can be selectively discharged. it can.
- the fuel for the burner is not particularly limited, and may be solid, liquid, or gas (gas).
- a solid fuel such as coke, coal, or pulverized coal
- a liquid fuel such as heavy fuel oil A or heavy fuel oil C
- a gas fuel such as LNG or LPG
- a burner (gas burner) using a gaseous fuel is particularly preferable because the combustion is relatively stable, the temperature can be easily controlled, and a high temperature can be realized.
- the heating using the burner is preferably performed by controlling the air-fuel ratio of the burner to a predetermined range.
- the mixture is heated by controlling the air-fuel ratio of the burner to a range of preferably 0.8 or more and 1.1 or less, more preferably 0.85 or more and 0.95 or less.
- the air-fuel ratio refers to a mass ratio of air to fuel.
- the reduction reaction can proceed in a short time and the mixture can be melted in a short time. Further, the generated molten metal and slag can be separated in a short time by the difference in specific gravity. For these reasons, the oxidation of the metal generated by the reduction reaction is relatively hard to proceed.
- the air-fuel ratio of the burner to a predetermined range, the oxygen concentration in the furnace atmosphere can be reduced, the oxidation of metal can be further suppressed, and high-quality fer nickel can be stably produced. It becomes possible.
- high-quality ferronickel can be stably manufactured by controlling the air-fuel ratio of the burner to preferably 0.8 to 1.1 and heating.
- the metal and the slag in the reduction treatment using a burner, it is preferable to heat the metal and the slag so that the respective temperatures of the obtained metal and slag are in the range of 1300 ° C. or more and 1700 ° C. or less.
- it is preferable to perform heating so that the temperature of the obtained metal is in the range of 1400 ° C to 1600 ° C, and the temperature of the slag is in the range of 1480 ° C to 1680 ° C.
- the temperature of the obtained metal and slag can be controlled by controlling the heating temperature by increasing or decreasing the amount of fuel heating in the burner.
- the recovery step S4 is a step of separating the metal obtained by the reduction and the slag to recover the metal.
- the recovery step S4 is a step of separating the metal obtained by the reduction and the slag to recover the metal.
- the reduction treatment in the reduction step S3 since the mixture using the burner is reduced in a molten state, molten metal and molten slag are generated. Since metal has a large specific gravity compared to slag, each metal is naturally separated due to a difference in specific gravity, and the metal accumulates at the bottom of the reduction furnace. Therefore, by extracting and collecting metal from the vicinity of the bottom of the reduction furnace, only metal can be selectively recovered.
- the slag floats on the metal, it can be withdrawn from the furnace wall and collected, for example. As described above, since the obtained metal and slag are in a molten state, they can be easily separated and recovered due to a difference in specific gravity.
- the metal and the slag may be collected in a mixed state from one hole of the reduction furnace.
- the structure of the reduction furnace can be simplified, and workability can be improved.
- the recovered metal and slag are cooled, solidified, and then separated by magnetic separation or the like, so that the metal can be recovered. Since the metal and slag are already separated when they are in a molten state, basically, the metal and the slag are kept separated even in a solid state. Can be recovered.
- FIG. 3 is a process diagram showing a flow of a method for smelting nickel oxide ore according to the second embodiment. As shown in FIG. 3, in the smelting method according to the second embodiment, unlike the smelting method according to the first embodiment, the drying step and the reduction step are performed together.
- the method for smelting nickel oxide ore according to the second embodiment includes a mixing step S11 of mixing a raw material containing nickel oxide ore, and charging the obtained mixture into a reduction furnace to perform a drying process.
- a drying / reducing step S12 for performing a reduction treatment is performed, and a recovery step S13 for separating the obtained reduced product metal and slag to recover the metal.
- the mixing step S11 and the recovery step S13 correspond to the mixing step S1 and the recovery step S4 in the smelting method according to the first embodiment, respectively, and perform the same processing. Is omitted. Also, regarding the processing in the drying / reducing step S12, the description of the contents common to the respective processing in the drying step S2 and the reducing step S3 in the smelting method according to the first embodiment is omitted, and only the different contents are omitted. This will be described in detail.
- drying / reducing step S12 a mixture containing at least the nickel oxide ore and the carbonaceous reducing agent obtained through the mixing step S11 is charged into a reduction furnace, and the mixture is subjected to a drying treatment in the reduction furnace. This is a step in which the subsequent mixture is reduced by heating with a burner by a continuous operation.
- a drying furnace directly connected to drying equipment is used, and drying and reduction are performed in the reducing furnace.
- the gas (exhaust gas) generated by performing the reduction treatment is directly introduced from the reduction furnace to the drying equipment, and the drying treatment is performed using the gas. Is performed.
- the gas generated by the reduction process is converted into a gas for drying the mixture. That is, it can be effectively used as a drying gas. This eliminates the need to secure a separate heat source for the drying process, and enables efficient operation.
- FIG. 4 is a view schematically showing a configuration example of a reduction furnace having a burner, and is a view (cross-sectional view) showing a configuration of a reduction furnace in which drying equipment is directly connected.
- the reduction furnace 20 includes a reduction processing unit 21 that heats the mixture M to perform a reduction process, and a drying processing unit 22 that performs a drying process on the mixture M prior to the reduction process in the reduction processing unit 21. , Is provided.
- the reduction processing section 21 and the drying processing section 22 are directly connected to each other to form a reduction furnace 20.
- the reduction furnace 20 includes a charging port 23 for charging the mixture M, and a discharging port 24 for discharging the metal obtained by the reduction process.
- the inner wall of the reduction furnace 20, especially the inner wall and the hearth of the reduction processing unit 21, be protected by slag coating.
- the mixture M charged from the charging inlet 23 is supplied to the drying processing unit 22.
- the drying processing unit 22 is configured by, for example, a belt conveyor device as shown in FIG. In the drying section 22, the supplied mixture M is placed on a belt of a belt conveyor device, and is subjected to a drying process while moving on the belt at a predetermined speed.
- the reduction processing unit 21 is provided with, for example, a burner 25 on the upper part thereof.
- the mixture (mixture after drying) M transferred through the drying processing in the drying processing section 22 is supplied, and the mixture M is heated by the burner 25 to a molten state, and included in the mixture M.
- the carbonaceous reducing agent causes a reduction reaction. That is, the reduction furnace 20 is a smelting reduction furnace. Inside the reduction processing section 21, metal and slag are generated by such a reduction reaction, and a reduced product in which the slag and the metal are separated into an upper layer and a lower layer, respectively, is obtained due to a difference in specific gravity.
- the reduction processing unit 21 and the drying processing unit 22 are directly connected to each other, as described above. More specifically, as shown in FIG. 4, in the positional relationship in the height direction, the drying processing unit 22 is located above and the reduction processing unit 21 is located below and are provided in the same space. Then, the reduction processing unit 21 and the drying processing unit 22 are connected in a state where they are communicated with each other. Accordingly, in such a reducing furnace 20, gas generated by the reduction processing in the reduction process unit 21 (exhaust gas) is, as indicated by the arrow G 1 in FIG. 4, by the upward flow, from the reduction processing unit 21 Are also introduced directly into the drying section 22 located above in the height direction.
- the drying process unit 22 in the reduction furnace 20 having such a configuration is performed drying processes using directly introduced gas from the reduction processing unit 21 as the drying gas (arrow G 2 in FIG. 4).
- the gas generated by the reduction processing in the reduction processing section 21 is an exhaust gas generated by the processing at a high reduction temperature, and is in a high temperature state. Therefore, it can be suitably used as a drying gas.
- the high-temperature gas is used as the drying gas, it is not necessary to perform heating again, and the cost can be effectively reduced.
- the gas obtained through the reduction treatment is a reducing gas. Therefore, by performing the drying treatment using the high-temperature gas having such a reducing property as the drying gas in the drying treatment unit 22, the oxidation of the mixture can be effectively prevented. Thereby, when the dried mixture M is subjected to the reduction treatment, a uniform reduction reaction can be generated without excess and deficiency, and a high-quality metal can be manufactured.
- Example 1 Comparative Example 1 >> (Mixing process) Nickel oxide ore and iron ore as raw material ores, silica sand and limestone as flux components, a binder, and a carbonaceous reducing agent (coal powder, carbon content: 82% by mass, average particle size: about 65 ⁇ m) were added to an appropriate amount of water. Was added using a mixer to obtain a mixture. The amount of the carbonaceous reducing agent required for reducing nickel oxide (NiO) and iron oxide (Fe 2 O 3 ) contained in the nickel oxide ore without excess or deficiency is 27% by mass. It was contained in such an amount as to be a percentage by mass.
- NiO nickel oxide
- Fe 2 O 3 iron oxide
- Example 1 (Drying process, reduction process) In Example 1, the obtained mixture was directly charged into a drying facility without being formed, subjected to a drying treatment at a temperature of 180 ° C. or more for 1 hour, and the dried mixture was subjected to a reduction furnace having a burner (burner furnace). ). A gas burner using a gaseous fuel was used as the burner. In the burner furnace, the charged mixture was heated by a burner to be in a molten state and subjected to a reduction treatment. By this reduction treatment, metal and slag in a molten state were generated in the burner furnace, and the slag was separated into an upper layer and the metal was separated into a lower layer due to a difference in specific gravity. In the reduction treatment, the operation was divided into Examples 1-1 to 1-5, and the mixture was heated so that the temperature of the obtained metal and slag became the temperature shown in Table 3 below as the reduction temperature in each operation. And reduced.
- Comparative Example 1 the obtained mixture was granulated by a bread granulator and sieved to a size of ⁇ 14.0 ⁇ 0.5 mm. Thereafter, a drying treatment was performed for 1 hour at a temperature of 180 ° C. or more in a drying facility. Thereafter, the dried sample was divided into four parts (Comparative Examples 1-1 to 1-4), and subjected to a reduction treatment using a rotary hearth furnace. In the reduction treatment, the reduction was performed so that the temperature in the furnace shown in Table 3 below was set as the reduction temperature.
- the reduction time refers to an average time from charging the mixture containing nickel oxide ore to the reduction furnace to discharging the generated molten metal and slag from the reduction furnace.
- Example 1 molten metal was extracted from the vicinity of the bottom of the burner furnace and collected.
- Comparative Example 1 the reduced product obtained after the reduction treatment was pulverized and then subjected to magnetic separation to collect the metal.
- Nickel metallization rate amount of metallized Ni in pellets ⁇ (amount of all nickel in pellets) ⁇ 100 (%)
- Nickel content in metal metallized Ni in pellets Amount ⁇ (Total amount of metalized nickel and iron in pellets) ⁇ 100 (%) ⁇ ⁇ ⁇ Equation (2)
- the nickel metal recovery rate was calculated by the following equation (3) from the nickel content in the nickel oxide ore subjected to the reduction treatment, the charged amount, and the recovered nickel amount.
- Nickel metal recovery rate recovered nickel amount / (amount of charged ore ⁇ nickel content in ore) ⁇ 100 (3)
- Comparative Examples 1-1 to 1-4 in which the reduction treatment was performed by the conventional method using a rotary hearth furnace, the nickel metallization rate, the nickel content in the metal, and the metal recovery rate were all the examples. It was a low value compared to. In the methods of Comparative Examples 1-1 to 1-4, the reduction time was longer than in the examples.
- Example 2 the drying treatment and the reduction treatment were performed using a reduction furnace (burner furnace) to which drying equipment was directly connected as illustrated in FIG. Specifically, after the mixture was charged into a reduction furnace, the mixture was dried using a gas generated by the reduction treatment in a drying facility (drying processing unit 22 in FIG. 4) as a drying gas. Thereafter, the dried mixture was heated and melted by a burner in the main body of the reduction furnace (reduction processing section 21 in FIG. 4). Otherwise, the operation was performed in the same manner as in Example 1.
- a reduction furnace burner furnace
- the molten metal is extracted from the vicinity of the bottom of the burner furnace and collected, and the obtained metal sample is analyzed for nickel metalization ratio, nickel content in metal (nickel grade), and metal recovery ratio. did. Table 4 below shows the analysis results.
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Abstract
Description
本発明は、例えばニッケル酸化鉱石等の酸化鉱石を原料として、その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還元することによって、還元物であるメタルを製造する酸化鉱石の製錬方法である。例えば、原料鉱石としてニッケル酸化鉱石を用いる場合、還元物として鉄のニッケルの合金であるフェロニッケルメタルを製造する。
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、原料鉱石にニッケル酸化鉱石を用い、そのニッケル酸化鉱石に含まれるニッケル(酸化ニッケル)と鉄(酸化鉄)とを還元することで、鉄-ニッケル合金(フェロニッケル)のメタルを生成させ、さらに、そのメタルを分離することによってフェロニッケルを製造する製錬方法を例に挙げて説明する。
図1は、ニッケル酸化鉱石の製錬方法の流れを示す工程図である。図1に示すように、本実施の形態(第1の実施形態)に係るニッケル酸化鉱石の製錬方法は、ニッケル酸化鉱石を含む原料を混合する混合工程S1と、得られた混合物を乾燥する乾燥工程S2と、乾燥後の混合物を所定の還元温度に加熱して還元する還元工程S3と、得られた還元物であるメタルとスラグとを分離してメタルを回収する回収工程S4と、を有する。
混合工程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、混合工程S1では、原料鉱石であるニッケル酸化鉱石と、炭素質還元剤とを混合し、また任意成分の添加剤として、鉄鉱石、フラックス成分、バインダー等の、例えば粒径が0.1mm~0.8mm程度の粉末を混合して混合物を得る。
乾燥工程S2は、得られた混合物を乾燥する工程である。本実施の形態においては、上述した混合工程S1を経て得られた混合物をそのまま、後述する還元炉に装入して還元処理(還元工程S3)を施してもよいが、還元処理に先立って混合物を乾燥させてもよい。なお、このように乾燥工程S2にて処理が施した場合、乾燥後の混合物が、還元炉に装入されて、次に還元工程S3における処理に供される。
還元工程S3は、混合物を還元炉に装入し、混合物を還元することによってメタルとスラグとを生成させる工程である。具体的に、本実施の形態に係るニッケル酸化鉱石の製錬方法では、バーナーを有する還元炉(以下、「バーナー炉」ともいう)を用い、混合物をバーナーにより加熱することによって酸化鉱石を還元する。このバーナーによる加熱還元処理では、還元反応の進行と共に混合物が溶融していき、溶融状態のメタルとスラグとが生成する。
回収工程S4は、還元により得られたメタルとスラグとを分離してメタルを回収する工程である。上述したように、還元工程S3における還元処理では、バーナーを用いた混合物を溶融状態にして還元するため、溶融メタルと溶融スラグとが生成する。メタルはスラグと比較して比重が大きく重いため、それぞれは比重差によって自然に分離し、メタルは還元炉の炉底に溜まる。そのため、還元炉の炉底付近からメタルを抜いて回収することで、メタルのみを選択的に回収することができる。一方、スラグはメタルの上に浮くため、例えば炉壁から抜いて回収することができる。このように、得られたメタルとスラグとは熔融状態にあるため、その比重差によって容易に分離させて回収することができる。
図3は、第2の実施形態に係るニッケル酸化鉱石の製錬方法の流れを示す工程図である。図3に示すように、第2の実施形態に係る製錬方法では、第1の実施形態に係る製錬方法とは異なり、乾燥工程と還元工程とを合わせて実行するようにしている。
乾燥・還元工程S12は、混合工程S11を経て得られたニッケル酸化鉱石と炭素質還元剤とを少なくとも含む混合物を還元炉に装入し、その還元炉内で混合物に対する乾燥処理を施すとともに、乾燥後の混合物を連続的な操作により、バーナーで加熱して還元する工程である。
(混合工程)
原料鉱石としてのニッケル酸化鉱石、鉄鉱石、フラックス成分である珪砂及び石灰石、バインダー、及び炭素質還元剤(石炭粉、炭素含有量:82質量%、平均粒径:約65μm)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、炭素質還元剤については、ニッケル酸化鉱石に含まれる酸化ニッケル(NiO)と酸化鉄(Fe2O3)とを過不足なく還元するのに必要な量を100質量%としたときに27質量%の割合となる量で含有させた。
実施例1では、得られた混合物を成形せずにそのまま乾燥設備に装入して180℃以上の温度で1時間の乾燥処理を施し、乾燥後の混合物を、バーナーを有する還元炉(バーナー炉)に装入した。バーナーとしては気体燃料を用いたガスバーナーを用いた。バーナー炉では、装入した混合物をバーナーにより加熱して溶融状態にして還元処理を施した。この還元処理により、バーナー炉では溶融状態にあるメタルとスラグとが生成し、比重差によってスラグが上層に、メタルが下層にそれぞれ分離した。なお、還元処理では、操業を実施例1-1~1-5に分け、それぞれの操業における還元温度として、得られるメタルとスラグの温度が下記表3に示す温度となるように混合物を加熱して還元した。
実施例1では、バーナー炉の炉底付近から溶融したメタルを抜き出して回収した。一方で、比較例1では、還元処理後に得られた還元物を粉砕し、その後磁選してメタルを回収した。
以上のようにして得られた各メタル試料について、ニッケルメタル化率、メタル中ニッケル含有量(ニッケル品位)、及びメタル回収率をそれぞれ分析した。下記表3に、分析結果を示す。また、表3には還元時間も併せて示す。
ニッケルメタル化率=ペレット中のメタル化したNiの量÷(ペレット中の全てニッケルの量)×100(%) ・・・(1)式
メタル中ニッケル含有率=ペレット中のメタル化したNiの量÷(ペレット中のメタルしたニッケルと鉄の合計量)×100(%) ・・・(2)式
ニッケルメタル回収率=回収されたニッケル量÷(装入した鉱石の量×鉱石中のニッケル含有割合)×100 ・・・(3)式
実施例2では、図4に例示するような、乾燥設備が直接連結された還元炉(バーナー炉)を用いて、乾燥処理と還元処理とを施した。具体的に、混合物を還元炉に装入した後、乾燥設備(図4における乾燥処理部22)において還元処理により発生したガスを乾燥用ガスとして用いて混合物を乾燥した。その後、乾燥後の混合物を還元炉の本体部(図4における還元処理部21)においてバーナーにより加熱して溶融させた。なお、それ以外は、実施例1と同様にして操業を行った。
11 処理部
21 還元処理部
22 乾燥処理部
12,23 装入口
13,24 排出口
14,25 バーナー
Claims (8)
- 酸化鉱石と炭素質還元剤との混合物を還元することによって還元物であるメタルを製造する酸化鉱石の製錬方法であって、
前記混合物を還元炉に装入し、該混合物をバーナーにより加熱することによって酸化鉱石を還元し、溶融状態のメタルとスラグとを得る還元工程を含む
酸化鉱石の乾式製錬方法。 - 前記酸化鉱石は、ニッケル酸化鉱石であり、
前記ニッケル酸化鉱石を含む混合物を還元することによってフェロニッケルを製造する
請求項1に記載の酸化鉱石の製錬方法。 - 前記還元工程では、酸化鉱石を還元することによって生成する溶融状態のメタルとスラグとを比重分離する
請求項1又は2に記載の酸化鉱石の製錬方法。 - 前記還元工程では、前記還元炉内で得られるメタルとスラグの温度がそれぞれ1300℃以上1700℃以下の範囲となるように前記混合物を加熱する
請求項1乃至3のいずれかに記載の酸化鉱石の製錬方法。 - 前記還元工程では、前記バーナーの空燃比を0.8以上1.1以下の範囲に制御して前記混合物を加熱する
請求項1乃至4のいずれかに記載の酸化鉱石の製錬方法。 - 前記混合物を乾燥する乾燥工程をさらに含み、
前記乾燥工程では、前記還元炉にて発生するガスを用いて前記混合物を乾燥し、乾燥後の混合物を前記還元工程における処理に供する
請求項1乃至5のいずれかに記載の酸化鉱石の製錬方法。 - 前記乾燥工程では、前記還元炉に直接連結された乾燥設備にて前記混合物を乾燥し、
前記乾燥設備には、前記還元工程での還元処理により前記還元炉にて発生するガスが該還元炉から直接導入される
請求項6に記載の酸化鉱石の製錬方法。 - 酸化鉱石と炭素質還元剤との混合物を溶融還元する溶融還元炉であって、
前記混合物を乾燥する乾燥処理部と、
バーナーを有し、前記乾燥処理部での乾燥後の混合物を該バーナーにより加熱することによって酸化鉱石を還元し、溶融状態のメタルとスラグとを得る還元処理部と、を備え、
高さ方向の関係において、前記乾燥処理部が上方に、前記還元処理部が下方に、それぞれ位置して同一空間内に設けられており、
前記乾燥処理部では、下方に位置する前記還元処理部にて発生したガスによって前記混合物を乾燥する
溶融還元炉。
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