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WO2025211235A1 - Procédé de production de minerai aggloméré contenant du carbone non cuit et procédé d'utilisation de biomasse d'acide silicique dans un haut-fourneau - Google Patents

Procédé de production de minerai aggloméré contenant du carbone non cuit et procédé d'utilisation de biomasse d'acide silicique dans un haut-fourneau

Info

Publication number
WO2025211235A1
WO2025211235A1 PCT/JP2025/012143 JP2025012143W WO2025211235A1 WO 2025211235 A1 WO2025211235 A1 WO 2025211235A1 JP 2025012143 W JP2025012143 W JP 2025012143W WO 2025211235 A1 WO2025211235 A1 WO 2025211235A1
Authority
WO
WIPO (PCT)
Prior art keywords
carbon
raw material
biomass
blast furnace
ore
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.)
Pending
Application number
PCT/JP2025/012143
Other languages
English (en)
Japanese (ja)
Inventor
哲也 山本
政洋 関屋
武司 堤
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.)
Nippon Steel Corp
Original Assignee
Nippon Steel Corp
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 Nippon Steel Corp filed Critical Nippon Steel Corp
Publication of WO2025211235A1 publication Critical patent/WO2025211235A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B5/00—Making pig-iron in the blast furnace
    • 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

Definitions

  • the present invention relates to a method for producing unfired carbon-containing agglomerates and a method for using silica biomass in a blast furnace.
  • Patent Document 1 discloses an invention in which the melting point of slag generated in the lower part of the furnace is lowered and air and liquid permeability are improved by adjusting the basicity, CaO/ SiO2, which is the ratio of gangue components in uncalcined carbon-bearing agglomerates, to 1.0 to 2.0, as shown in Figure 1. Furthermore, this document states that in order to adjust the basicity, CaO/ SiO2, of uncalcined carbon-bearing agglomerates to 1.0 to 2.0, it is preferable to adjust the blending amount of ore with a high SiO2 content (also called silicic acid-containing ore).
  • a high SiO2 content also called silicic acid-containing ore
  • Patent Document 2 discloses an invention related to PCI (Pulverized Coal Injection), a pulverized coal injection technology in which biochar obtained by carbonizing biomass is pulverized into pulverized coal PC (Pulverized Coal), which is then injected into the blast furnace through the blast tuyeres 3 (see Figure 2).
  • PCI Pulverized Coal Injection
  • PC Pulverized Coal
  • biomass also known as silicate biomass due to its high ash content
  • biomass such as rice husks and straw
  • biochar derived from silicate biomass can be problematic due to its high ash content of around 30-50%.
  • biochar derived from silicate biomass not only promises a stable supply, but also has sufficient properties as a carbon source, with a fixed carbon content of around 15-50% and a unit calorific value of around 14-28 MJ/kg.
  • the present invention therefore aims to provide a method for producing unfired carbon-bearing agglomerates that utilizes biochar derived from silicate biomass, and a method for using silicate biomass in a blast furnace.
  • a method for producing unfired carbon-bearing agglomerates by forming a blended raw material containing an iron-bearing raw material, a carbon-bearing raw material, a gangue raw material, and a binder into an agglomerate and curing it for a predetermined period of time, A method for producing unfired carbon-containing agglomerates, in which part or all of the carbon-containing raw material and part or all of the siliceous ore in the gangue raw material are replaced with fixed carbon and silicon oxide in biochar obtained by dry distillation of siliceous biomass.
  • the method for utilizing silica biomass in a blast furnace comprises forming the blended raw material into an agglomerate, curing the agglomerate for a predetermined period of time, and then charging the resulting uncalcined carbon-containing agglomerate into the top of the blast furnace.
  • biochar derived from silicic acid biomass which is produced in large quantities in Japan every year, can be used as the raw material for uncalcined carbon-bearing agglomerates, containing both the carbon-bearing raw materials and the gangue raw materials, thereby providing an advantage in terms of procurement.
  • a new use can be provided for biochar derived from silicic acid biomass, which has previously had limited uses due to its high ash content, by effectively utilizing both fixed carbon and silicon oxide.
  • the present invention can provide a method for producing unsintered carbon-bearing agglomerates and a method for using silica biomass in a blast furnace, which contribute to the procurement of biochar and the reduction of CO2 emissions in the steel industry without adversely affecting the air and liquid permeability in the cohesive zone at the bottom of the furnace.
  • FIG. 1 is a graph showing the relationship between CaO/SiO 2 and metal dropping rate of unsintered carbon-containing agglomerates disclosed in Patent Document 1.
  • FIG. 1 is a schematic vertical cross-sectional view of a blast furnace for explaining an overview of the process for producing molten iron from iron ore in a blast furnace. 1 is a flow chart for explaining a method for producing unburned carbon-containing agglomerates according to an embodiment of the present invention.
  • a donut-shaped cohesive zone 4 is formed in a semi-molten state with a high density somewhere between solid and liquid.
  • This cohesive zone 4 acts as a straightening plate for the high-temperature gas rising from below. Because a relatively large amount of high-temperature gas flows through the relatively thin iron ore layer in the center, the fused layer forms preferentially from the upper center of the furnace, and the piled-up layers take on an inverted V shape.
  • the high-temperature gas rising inside the furnace flows along the inverted V-shaped cohesive zone 4 toward the upper center, and the gas that has gathered at the central axis is evenly redistributed to the periphery of the furnace via the coke layer.
  • the unsintered carbon-containing agglomerates according to the embodiment of the present invention are produced by forming agglomerates from a blend of raw materials containing an iron-containing raw material, a carbon-containing raw material, a gangue raw material, and a binder, and curing the agglomerates for a predetermined period of time.
  • the predetermined curing period can be, for example, about one to three weeks.
  • some or all of the carbon-containing raw material and some or all of the siliceous ore in the gangue raw material are replaced with fixed carbon and silicon oxide in biochar obtained by dry distillation of siliceous biomass.
  • the method for utilizing silica biomass in a blast furnace in which the uncalcined carbon-containing agglomerate produced in this manner is charged into the top of the blast furnace, is another embodiment of the present invention. Note that, here, the two methods will be described together without distinguishing between them.
  • a blend of iron-containing, carbon-containing, and gangue raw materials is mixed in a ball mill while adjusting the particle size distribution to an appropriate range before kneading.
  • the fixed carbon of the carbon-containing raw material and the ash of the gangue raw material are already mixed, but this is not a problem.
  • the silicic acid biomass-derived biochar of this embodiment is also mixed with other blended raw materials, such as iron-containing raw materials, while undergoing particle size adjustment through conventional processes. A binder and approximately 5 to 15% moisture, depending on the binder amount, are then added to the blended raw materials and kneaded in a mixer.
  • the blended raw materials are then granulated using a pan pelletizer (also known as a disc pelletizer) and formed into pellets.
  • a pan pelletizer also known as a disc pelletizer
  • the green pellets after molding are typically cured for approximately two weeks in the case of sun curing, but this is not limited to this period and can be adjusted to a period of approximately one to three weeks depending on the raw material blend ratio, curing conditions such as temperature and humidity, and the required properties of the agglomerated ore.
  • iron-containing raw materials used in this embodiment include iron-containing dust such as sinter dust and blast furnace dust generated in the steelmaking process, pellet feed with a smaller particle size than fine iron ore for sintering, fine iron ore produced by crushing and/or sizing fine iron ore for sintering, etc. Recycling of various iron-containing dusts recovered from steelworks and effective use of fine iron ore (fine iron ore) not used as sinter can contribute to reducing CO2 emissions.
  • iron-containing dust such as sinter dust and blast furnace dust generated in the steelmaking process
  • pellet feed with a smaller particle size than fine iron ore for sintering fine iron ore produced by crushing and/or sizing fine iron ore for sintering, etc. Recycling of various iron-containing dusts recovered from steelworks and effective use of fine iron ore (fine iron ore) not used as sinter can contribute to reducing CO2 emissions.
  • Silicate biomass refers to plants containing silica (silica plants) or parts thereof such as their leaves and stems, and includes rice and wheat husks and straw, bamboo leaves, and corn leaves and stems.
  • Biochar derived from siliceous biomass is a carbonaceous material obtained by dry distilling siliceous biomass. The dry distillation method is not important, but dry distillation using a rotary kiln is an example. As mentioned above, biochar derived from siliceous biomass has a fixed carbon content of approximately 15-50%, an ash content of approximately 30-50%, and a unit calorific value of approximately 14-28 MJ/kg.
  • the basicity of the molten liquid of all the raw materials charged to the blast furnace is usually adjusted by increasing or decreasing the amount of auxiliary materials mixed with raw materials such as iron ore so that it falls within a predetermined range. It is also preferable to control the basicity of the molten liquid of the unsintered carbon-containing agglomerates alone so that it falls within a predetermined range, for example, as shown in Figure 1. However, since the basicity of the molten liquid in the blast furnace is also adjusted by the auxiliary materials of the other raw materials charged to the blast furnace, there are cases where adjustment of the unsintered carbon-containing agglomerates alone is not necessary.
  • Gangue components in gangue raw materials commonly used in non-calcined carbon-bearing agglomerates include CaO, SiO 2 , Al 2 O 3 , MgO, etc. These components are also contained in the iron-bearing raw materials, the carbon-bearing raw materials, and the binder.
  • unsintered carbon-bearing agglomerates use hydraulic binders such as CaO-based cement to provide the agglomerates with sufficient cold crushing strength.
  • binders can include commonly used fine powders primarily composed of granulated blast furnace slag, time-aging binders made from alkaline activators, quicklime, Portland cement, bentonite, and the like.
  • the amount of binder can be determined appropriately, taking into account other blending conditions, etc. If the amount of binder is too small, it becomes difficult to maintain sufficient cold crushing strength of the unsintered carbon-bearing agglomerates.
  • the binder components of unsintered carbonaceous agglomerates increase the basicity CaO/ SiO2 of the melt of the unsintered carbonaceous agglomerates, which may impair the air permeability and liquid permeability around the cohesive zone of the blast furnace.
  • gangue components are also contained in the iron-bearing raw materials and the carbonaceous raw materials, the basicity CaO/ SiO2 is increased mainly due to the binder components. Therefore, a silicic acid-containing ore such as silica stone is blended into the unsintered carbonaceous agglomerates according to this embodiment as a gangue raw material to reduce this basicity.
  • Silica stone is a typical example of the silicic acid-containing ore, but it is not limited thereto.
  • this siliceous ore is used as the gangue raw material by replacing the silicon oxide in biochar derived from siliceous biomass without changing the gangue content charged to the blast furnace. Therefore, even if biochar derived from siliceous biomass is used in unfired carbon-bearing agglomerates, there is no adverse effect on the air and liquid permeability in the cohesive zone at the bottom of the furnace.
  • the content of gangue components such as SiO2 varies greatly depending on the brand of original ore, such as the ore that generates dust and the ore that is blended into sintered ore, it is preferable to adjust the CaO/ SiO2 value by selecting the brand of ore used in the steelworks.
  • the CaO/ SiO2 value is greatly affected by the blending amount of ore with a high SiO2 content.
  • This section describes a preferred embodiment of the method for producing uncalcined carbonaceous agglomerates that utilizes biochar derived from silicic acid biomass.
  • the fixed carbon content and ash content per unit amount of biochar derived from silicic acid biomass are expected to fluctuate.
  • the fixed carbon content and ash content per unit amount of the incoming biochar derived from silicic acid biomass are confirmed.
  • the confirmed fixed carbon content is sufficient to replace the entire amount of the carbonaceous raw material in the raw material mix for uncalcined carbonaceous agglomerates. If the amount is insufficient, the biochar is changed to partial replacement, and the raw material mix ratio is determined.
  • the silicon oxide content in the biochar that is ultimately included in the uncalcined carbonaceous agglomerates is used as part or all of the silicic acid ore in the gangue raw material for the uncalcined carbonaceous agglomerates.
  • the amount of silicon oxide in the biochar derived from silicic acid biomass may affect the basicity of the melt in the blast furnace. Therefore, adjusting the basicity of the uncalcined carbonaceous agglomerates alone is preferable, but is not essential, as it can also be adjusted using a separate auxiliary raw material in the blast furnace charge.
  • the blended raw materials are assumed to consist of only three types: biochar (A (tons), fine iron ore (B (tons), and binder (C (tons)), and the sum of these amounts is assumed to be D (tons) of unfired carbon-bearing agglomerate ore.
  • A+B+C D...
  • a typical reduction reaction of iron ore is as follows: Fe 2 O 3 +3/2C ⁇ 2Fe+3/2CO 2 ... (2) From the reaction formula (2), it can be seen that theoretically, 3/2 moles of carbon are required per mole of iron ore, but here, 3 moles of carbon are blended per mole of iron ore, taking into consideration reaction yield, etc. In addition, the calculation is premised on the atomic weight of carbon being 12 and the molecular weight of iron ore (Fe 2 O 3 ) being 160.
  • the biochar derived from silicate biomass is rice husk charcoal dry-distilled at 500°C, and its specific components are as follows: ⁇ Fixed carbon: 28.0% by mass Volatile content: 34.5% by mass ⁇ Ash content: 37.5% by mass (including SiO 2 : 33.6% by mass)
  • the amount of binder to be mixed is usually about 3 to 10 mass % of the total amount of the carbonaceous material and the iron ore powder, but here it is set to 10 mass %, and taking into account formula (3), it is set as shown in the following formula (4).
  • C 1.22A... (4)
  • formula (9) shows that it is possible to reduce the amount of sintered ore by 0.836 times the weight of the agglomerates a (ton) that are replaced with silica stone (33.4 times the weight of the auxiliary raw material silica stone b (ton)).

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Geology (AREA)
  • Mechanical Engineering (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

La présente invention concerne un procédé de production de minerai aggloméré contenant du carbone non cuit et un procédé d'utilisation de biomasse d'acide silicique dans un haut-fourneau dans chacun desquels du charbon de biomasse dérivé de biomasse d'acide silicique est utilisé. Dans la présente invention se rapportant à un procédé de production de minerai aggloméré contenant du carbone non cuit, une matière première combinée contenant une matière première contenant du fer, une matière première contenant du carbone, une matière première de gangue et un liant est utilisée pour mouler un article aggloméré, l'article aggloméré est durci pendant une période de temps prescrite, et ainsi du minerai aggloméré contenant du carbone non cuit est produit. À ce stade, du carbone et de l'oxyde de silicium fixés dans du charbon de biomasse qui est obtenu par carbonisation de biomasse d'acide silicique sont utilisés, dans la matière première combinée utilisée, en tant que partie ou totalité de la matière première contenant du carbone et une partie ou la totalité du minerai contenant de l'acide silicique dans la matière première de gangue. Dans la présente invention se rapportant à un procédé d'utilisation de biomasse d'acide silicique dans un haut-fourneau, le minerai aggloméré contenant du carbone non cuit obtenu comme décrit ci-dessus est chargé par le haut du haut-fourneau.
PCT/JP2025/012143 2024-04-01 2025-03-26 Procédé de production de minerai aggloméré contenant du carbone non cuit et procédé d'utilisation de biomasse d'acide silicique dans un haut-fourneau Pending WO2025211235A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2024059017 2024-04-01
JP2024-059017 2024-04-01

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WO2025211235A1 true WO2025211235A1 (fr) 2025-10-09

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6250420A (ja) * 1985-08-28 1987-03-05 Nippon Steel Corp 非焼成塊成鉱
JP2002146444A (ja) * 2000-08-30 2002-05-22 Kobe Steel Ltd 製鉄原料の塊成化物製造方法
JP2009057438A (ja) * 2007-08-31 2009-03-19 Tohoku Univ 半乾留バイオマス微粉炭材の製造方法および半乾留バイオマス微粉炭材の使用方法
WO2011021577A1 (fr) * 2009-08-21 2011-02-24 新日本製鐵株式会社 Agglomérat à teneur en carbone, non cuit, pour des hauts-fourneaux et son procédé de fabrication
JP2011117075A (ja) * 2009-10-29 2011-06-16 Jfe Steel Corp バイオマスの高炉利用方法
WO2023199550A1 (fr) * 2022-04-11 2023-10-19 Ｊｆｅスチール株式会社 Procédé de fonctionnement pour haut-fourneau

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6250420A (ja) * 1985-08-28 1987-03-05 Nippon Steel Corp 非焼成塊成鉱
JP2002146444A (ja) * 2000-08-30 2002-05-22 Kobe Steel Ltd 製鉄原料の塊成化物製造方法
JP2009057438A (ja) * 2007-08-31 2009-03-19 Tohoku Univ 半乾留バイオマス微粉炭材の製造方法および半乾留バイオマス微粉炭材の使用方法
WO2011021577A1 (fr) * 2009-08-21 2011-02-24 新日本製鐵株式会社 Agglomérat à teneur en carbone, non cuit, pour des hauts-fourneaux et son procédé de fabrication
JP2011117075A (ja) * 2009-10-29 2011-06-16 Jfe Steel Corp バイオマスの高炉利用方法
WO2023199550A1 (fr) * 2022-04-11 2023-10-19 Ｊｆｅスチール株式会社 Procédé de fonctionnement pour haut-fourneau

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