WO2024070135A1 - 鉄鉱石ペレットの製造方法 - Google Patents

鉄鉱石ペレットの製造方法 Download PDF

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Publication number
WO2024070135A1
WO2024070135A1 PCT/JP2023/025632 JP2023025632W WO2024070135A1 WO 2024070135 A1 WO2024070135 A1 WO 2024070135A1 JP 2023025632 W JP2023025632 W JP 2023025632W WO 2024070135 A1 WO2024070135 A1 WO 2024070135A1
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Prior art keywords
gas
iron ore
carbon
pellets
solid carbon
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PCT/JP2023/025632
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English (en)
French (fr)
Japanese (ja)
Inventor
健太 竹原
隆英 樋口
勇介 土肥
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Ｊｆｅスチール株式会社
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Application filed by Ｊｆｅスチール株式会社 filed Critical Ｊｆｅスチール株式会社
Priority to AU2023352518A priority Critical patent/AU2023352518A1/en
Priority to EP23871379.6A priority patent/EP4575020A4/en
Priority to CN202380065653.5A priority patent/CN119866382A/zh
Priority to JP2024504885A priority patent/JPWO2024070135A1/ja
Publication of WO2024070135A1 publication Critical patent/WO2024070135A1/ja

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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
    • C22B1/16—Sintering; Agglomerating
    • 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
    • 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
    • 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
    • C22B1/2406—Binding; Briquetting ; Granulating pelletizing
    • 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
    • C22B1/2413—Binding; Briquetting ; Granulating enduration of pellets
    • 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
    • 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
    • C22B1/244—Binding; Briquetting ; Granulating with binders organic
    • C22B1/245—Binding; Briquetting ; Granulating with binders organic with carbonaceous material for the production of coked agglomerates

Definitions

  • the present invention relates to a method for producing iron ore pellets.
  • Iron ore pellets are produced by granulating iron ore powder to have properties (e.g., size, strength, reducibility, etc.) suitable for feeding into a blast furnace or a solid reduction furnace. Iron ore pellets are generally produced by the following steps: mixing iron ore powder, a binder, and any auxiliary material to obtain a mixture; granulating the mixture to obtain green pellets; and firing the green pellets to obtain iron ore pellets. In this specification, pellets as granulated before firing are referred to as "green pellets.”
  • a carbonaceous material such as anthracite
  • the firing step natural gas containing CH4 gas as a main component is burned to heat the green pellets, and the heat generated by this combustion is transferred from the surface of the green pellets to the inside. For this reason, the heating inside the pellets may be insufficient, leading to a decrease in strength. Therefore, in order to compensate for the heat inside the pellets, a carbonaceous material such as anthracite is added to the green pellets, and the carbonaceous material is burned in the firing step to heat the green pellets from the inside.
  • a carbonaceous material such as anthracite is added to the green pellets, and the carbonaceous material is burned in the firing step to heat the green pellets from the inside.
  • silicates sodium silicate, calcium silicate
  • silicates are listed as inorganic binders, but silicate itself needs to be separated as slag from pig iron or molten steel in either the pig iron making or steel making process, and excess heat is required to melt the pig iron.
  • the inorganic binder is discharged as slag, i.e., excess material.
  • the present invention aims to provide a method for producing iron ore pellets that can produce high-strength iron ore pellets and contribute to carbon neutrality.
  • the present inventors have focused on improving the carbonaceous material added to the green pellets. That is, they have come up with the idea of using solid carbon containing carbon generated from one or more selected from the group consisting of CO2 gas, CO gas, and CH4 gas as the carbonaceous material added to the green pellets.
  • CO2 is generated by burning the carbonaceous material
  • the above-mentioned greenhouse gas is consumed as the raw material of the carbonaceous material, which contributes to carbon neutrality.
  • the gist of the present invention which was completed based on the above findings, is as follows:
  • the method for producing iron ore pellets of the present invention makes it possible to obtain high-strength iron ore pellets and contributes to carbon neutrality.
  • 1 shows a schematic diagram of a vertical reactor used in a carbon production test using CO gas as a raw material. Photographs showing the appearance of (a) sintered ore and (b) solid carbon after a carbon generation test are shown. 1(a) and (b) show schematic diagrams of an apparatus used in a carbon production test using CH4 gas as a raw material. 6(a) to 6(c) show the results of TEM observation of the solid carbon obtained in each carbon production test.
  • the method for producing iron ore pellets includes a mixing step of mixing iron ore, solid carbon (carbonaceous material), binder, and auxiliary materials to obtain a mixture, a granulation step of granulating the mixture to obtain green pellets, and a firing step of burning the solid carbon to heat the green pellets from the inside while burning CH4 gas to heat the green pellets from the outside to obtain iron ore pellets.
  • the solid carbon is characterized in that it contains carbon generated from one or more selected from the group consisting of CO2 gas, CO gas, and CH4 gas.
  • the mixture used to manufacture iron ore pellets consists of iron ore, solid carbon, binder, and auxiliary materials.
  • the iron ore contains iron with a total Fe content (T.Fe) of 63% by mass or less. Iron ore with a T.Fe content of 63% by mass or less is inexpensive and suitable for manufacturing.
  • the amount of solid carbon in the iron ore pellets is preferably 0.80% by mass or more relative to the amount of iron ore in the iron ore pellets in order to fully obtain the strength-improving effect of the green pellets.
  • the amount of solid carbon in the iron ore pellets is preferably 2.00% by mass or less relative to the amount of iron ore in the iron ore pellets.
  • the solid carbon includes carbon generated from one or more selected from the group consisting of CO2 gas, CO gas, and CH4 gas. That is, carbon generated from one or more selected from the group consisting of CO2 gas, CO gas, and CH4 gas is used as the carbonaceous material (solid carbon) to be added to the green pellets.
  • CO2 is generated by burning the carbonaceous material
  • the greenhouse gas is consumed as the raw material of the carbonaceous material, which contributes to carbon neutrality.
  • carbon generated from one or more selected from the group consisting of CO2 gas, CO gas, and CH4 gas to the green pellets, the effect of increasing the strength of the green pellets and iron ore pellets can be obtained.
  • the proportion of the above carbon in the solid carbon added to the green pellets is preferably 10 mass% or more, more preferably 50 mass% or more, and most preferably 100 mass%.
  • the greater the amount of the above carbon the greater the effect of increasing strength and the greater the contribution to carbon neutrality.
  • the proportion of the above carbon in the solid carbon added to the green pellets is less than 100 mass%, the remainder of the solid carbon may be, for example, anthracite.
  • the solid carbon preferably contains carbon generated from one or both of CO2 gas and CO gas.
  • the CH4 gas used in generating the carbon preferably contains CH4 gas generated from one or both of CO2 gas and CO gas.
  • the reaction for generating solid carbon from CO2 gas, CO gas, or CH4 gas is not particularly limited, but examples of the reaction include the following.
  • Solid carbon may be produced from CO gas by the Boudouard reaction shown in reaction formula (1).
  • the Boudouard reaction makes it possible to produce solid carbon from CO gas at temperatures of about 700° C. or lower.
  • 2CO C+ CO2 (1)
  • Solid carbon may be produced from CO gas by the reverse water-gasification reaction shown in reaction formula (2).
  • the reverse water-gasification reaction makes it possible to produce solid carbon from CO gas at approximately 650° C. or lower.
  • CO + H 2 C + H 2 O ...
  • CH4 gas may be produced from CO gas by the methanation reaction shown in reaction formula (3), and solid carbon may be produced from CH4 gas by the thermal decomposition reaction shown in reaction formula (4).
  • the methanation reaction can produce CH4 gas from CO gas at approximately 650°C or lower, and the thermal decomposition reaction can produce solid carbon from CH4 gas in air at approximately 500°C or higher.
  • CO+ 3H2 CH4 + H2O ... (3)
  • CH4 C+ 2H2 ... (4)
  • Solid carbon may be produced from CO gas by the decomposition reaction shown in reaction formula (5).
  • Solid carbon may be produced from CO2 gas by the reverse water-gasification reaction shown in reaction formula (6).
  • the reverse water-gasification reaction can produce solid carbon from CO2 gas at approximately 650° C. or lower.
  • CO 2 + 2H 2 C + 2H 2 O ... (6)
  • CO gas may be produced from CO2 gas by the reverse water gas shift reaction shown in reaction formula (7), and solid carbon may be produced from CO gas by the reverse water gasification reaction shown in reaction formula (2).
  • the reverse water gas shift reaction can produce CO gas from CO2 gas at about 850°C or higher.
  • CO 2 + H 2 CO + H 2 O ... (7)
  • CO + H 2 C + H 2 O ... (2)
  • the methanation reaction shown in reaction formula (8) may generate CH4 gas from CO2 gas, and the thermal decomposition reaction shown in reaction formula (4) may generate solid carbon from CH4 gas.
  • the methanation reaction can generate CH4 gas from CO2 gas at approximately 600°C or lower.
  • CO2 + 4H2 CH4 + 2H2O ...
  • CH4 C+ 2H2 ... (4)
  • Solid carbon may be produced from CO2 gas by the decomposition reaction shown in reaction formula (9).
  • the decomposition reaction can produce solid carbon from CO2 gas under low oxygen partial pressure.
  • CO2 C + O2 ... (9)
  • Solid carbon may be produced from CH4 gas by the pyrolysis reaction shown in reaction formula (4).
  • CH4 C+ 2H2 ... (4)
  • the gas used in the carbon production reaction may be any one of CO2 gas, CO gas, or CH4 gas, a mixed gas of two or more of the above three types of gases, or a mixed gas of one or more of the above three types of gases with H2 gas, N2 gas, etc.
  • a mixed gas of CO: 31%, H2 : 19%, and N2 : 50% by volume may be used.
  • any one of carbon produced from CO2 gas, carbon produced from CO gas, and carbon produced from CH4 gas may be used alone, or two or more of them may be mixed and used.
  • the solid carbon is preferably produced using iron as a catalyst. It is known that iron can be used as a catalyst in the Boudouard reaction shown in reaction formula (1) and the thermal decomposition reaction of CH4 shown in reaction formula (4). It is also known that iron oxide can be used as a catalyst in the reverse water gas shift reaction shown in reaction formula (7). Therefore, when producing solid carbon, sintered ore or direct reduced iron may be charged into a furnace, and the iron or iron oxide contained in the sintered ore or direct reduced iron may be used as a catalyst. In addition, in a high-temperature reaction such as the thermal decomposition reaction of CH4 shown in reaction formula (4), alumina may be charged into the furnace to maintain the temperature inside the furnace.
  • the solid carbon is preferably in a fibrous form, and preferably has an aspect ratio (length/diameter) of 10 or more.
  • the solid carbon may also be in a spherical form.
  • the binder effect of the fine particles is obtained, and the strength of the iron ore pellets is preferably obtained.
  • the cumulative particle size D90 is preferably about 10 to 50 ⁇ m.
  • the solid carbon (carbon material) generated from one or more selected from the group consisting of CO2 gas, CO gas, and CH4 gas preferably has a carbon content of 50 mass% or more, and the balance may contain Fe, FeO, etc.
  • Bentonite is preferred as a binder for iron ore pellets, but any known or arbitrary binder that provides a similar effect, such as organic or inorganic binders, may also be used.
  • the binder be contained in an amount of 0.1 mass% or more relative to the amount of iron ore in the iron ore pellets.
  • the binder be contained in an amount of 4.0 mass% or less relative to the amount of iron ore in the iron ore pellets.
  • the iron ore pellets may be mixed with auxiliary materials such as quicklime, limestone (CaCO 3 ), and dolomite (CaMg(CO 3 ) 2 ).
  • the basicity of the iron ore pellets is adjusted by the auxiliary materials.
  • the basicity of the iron ore pellets is calculated based on the weight ratio of CaO/SiO 2 contained in the iron ore pellets.
  • the basicity of the iron ore pellets is preferably 0.01 to 1.5.
  • the iron ore pellets are manufactured by the general crushing, mixing, granulation, and firing processes.
  • the crushing process may use a crusher such as a general ball mill.
  • the mixing process may use a general concrete mixer or high-speed agitating mixer.
  • the granulation process may use a general pelletizer or drum mixer.
  • the Blaine index of the iron ore after pulverization is preferably about 2000 to 4000 cm2 /g.
  • the Blaine index is measured using a Blaine air permeability device specified in JIS R 5201:2015 and represents the specific surface area of the powder. In the pellet manufacturing process, the Blaine index is used as a control index for the particle size of the ore, and the higher this value, the finer the powder.
  • the granulated green pellets preferably have a particle size of about 9.5 to 12 mm. If the particle size of the green pellets is less than 9.5 mm, the air permeability will be reduced when they are filled into a blast furnace as fired pellets. If the particle size of the green pellets exceeds 12 mm, the reducibility will decrease.
  • the firing step may be performed using a general rotary kiln or electric furnace.
  • CH4 gas is burned to heat the green pellets from the outside, while solid carbon is burned to heat the green pellets from the inside.
  • the firing conditions are preferably a furnace temperature of 1200 to 1350°C and a holding time at the furnace temperature of 5 to 30 minutes.
  • the CH4 gas used in the calcination step preferably contains CH4 gas generated from one or both of CO2 gas and CO gas.
  • CH4 gas generated from one or both of CO2 gas and CO gas.
  • the method for generating CH4 gas may be generated, for example, by the methanation reaction shown in reaction formulas (3) and (8).
  • CO2 + 4H2 CH4 + 2H2O ...
  • CO+ 3H2 CH4 + H2O ... (3)
  • Iron ore, binder, and auxiliary materials were prepared as raw materials for iron ore pellets.
  • the components of the iron ore used are shown in Table 1.
  • the iron ore was dried at 105°C for 24 hours and then crushed to obtain iron ore powder with a Blaine index of 2560 cm2 /g and a volume average diameter of 95 ⁇ m.
  • Bentonite was prepared as the binder, and limestone was prepared as the auxiliary material.
  • anthracite was prepared as solid carbon that was not generated from any of CO gas, CO2 gas, and CH4 gas.
  • the anthracite was prepared in particulate form with a particle size of 1 mm or less and a C content of 85 mass%.
  • FIG. 1 shows a schematic diagram of a vertical reactor.
  • An alumina support 12, an alumina ball 14, and sintered ore 16 were charged in the order shown in the figure into a furnace core tube 10 with an inner diameter of ⁇ 80 mm.
  • a gas containing 31% CO, 19% H 2 , and 50% N 2 (hereinafter referred to as CO mixed gas) was introduced from a gas inlet tube 18 at 550°C or 800°C (heated by a heater 20, measured by a thermocouple 22) for 3 hours at a gas flow rate of 17 L/min to generate solid carbon.
  • the iron contained in the sintered ore was used as a catalyst for carbon generation.
  • FIG. 1 shows photographs of (a) sintered ore and (b) solid carbon after a carbon generation test from CO mixed gas at 800°C.
  • the solid carbon is a fine powder, and the cumulative particle sizes were measured to be D10: 2.1 ⁇ m, D50: 6.61 ⁇ m, and D90: 14.8 ⁇ m. In other words, more than 90% of the cumulative number of powder particles had a particle size of 14.8 ⁇ m or less.
  • Table 2 shows the results of the component analysis of the solid carbon.
  • Carbon production test from CH4 gas Carbon was generated from CH4 gas using the apparatus shown in Figures 3(a) and (b). First, 30 g (about 20 to 30 pieces) of direct reduced iron (DRI) 32 obtained by reducing iron ore pellets having a diameter of 10 mm as a catalyst was charged into the electric furnace 30 shown in Figure 3(a), and 100% CH4 gas was flowed in from the gas inlet 34 under the conditions of 900 ° C. for 1 h and a gas flow rate of 1.0 L / min to generate solid carbon.
  • DRI direct reduced iron
  • alumina balls 38 having a diameter of 6 mm were charged into the furnace core tube (alumina tube) 36 having a diameter of 80 mm shown in Figure 3(b), a uniform zone having a height of about 50 mm was formed, and 100% CH4 gas was flowed in from the gas inlet 40 under the conditions of a gas temperature of 1400 ( ⁇ 10) ° C. (heated by a heater 42) for 1 h and a gas flow rate of 1.0 L / min to generate solid carbon.
  • the reduced samples obtained in each test were sieved through a 0.125 mm sieve to separate the DRI or alumina balls from the solid carbon.
  • Table 3 shows the morphology and carbon content of the solid carbon and anthracite produced under each condition.
  • FIG. 4 shows the TEM observation results of (a) solid carbon produced from CO mixed gas at 550°C, (b) solid carbon produced from CH4 gas at 900°C, and (c) solid carbon produced from CH4 gas at 1400°C.
  • the solid carbon obtained in the reaction at 900°C or less was fibrous and had an aspect ratio of 10 or more.
  • the solid carbon obtained in the reaction at 1400°C was spherical and had a particle size of about 0.2 to 2.0 ⁇ m.
  • Green pellets not used in the above test were charged into an electric furnace and fired. In an air atmosphere, the temperature was raised at 10°C/min, held at 1300°C for 10 minutes, and then lowered at 10°C/min. After lowering the temperature, the sample was taken out to obtain iron ore pellets. In the firing process in actual operation, natural gas mainly composed of CH4 gas is burned to heat the green pellets, but in this test, an electric furnace was used to simulate this heating.
  • the present invention provides a method for producing iron ore pellets that can produce high-strength iron ore pellets and contribute to carbon neutrality.
  • furnace core tube 12 alumina support 14 alumina ball 16 sintered ore 18 gas inlet tube 20 heater 22 thermocouple 30 electric furnace 32 DRI reduced from iron ore pellets 34 Gas inlet 36 Furnace core tube 38 Alumina ball 40 Gas inlet 42 Heater

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PCT/JP2023/025632 2022-09-28 2023-07-11 鉄鉱石ペレットの製造方法 WO2024070135A1 (ja)

Priority Applications (4)

Application Number Priority Date Filing Date Title
AU2023352518A AU2023352518A1 (en) 2022-09-28 2023-07-11 Method of producing iron ore pellets
EP23871379.6A EP4575020A4 (en) 2022-09-28 2023-07-11 PROCESS FOR PRODUCING IRON ORE PELLETS
CN202380065653.5A CN119866382A (zh) 2022-09-28 2023-07-11 铁矿石球团的制造方法
JP2024504885A JPWO2024070135A1 (enrdf_load_stackoverflow) 2022-09-28 2023-07-11

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JP2022-155599 2022-09-28

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EP (1) EP4575020A4 (enrdf_load_stackoverflow)
JP (1) JPWO2024070135A1 (enrdf_load_stackoverflow)
CN (1) CN119866382A (enrdf_load_stackoverflow)
AU (1) AU2023352518A1 (enrdf_load_stackoverflow)
WO (1) WO2024070135A1 (enrdf_load_stackoverflow)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56123332A (en) * 1980-03-01 1981-09-28 Kobe Steel Ltd Calcining method for iron ore pellet
JP2021165214A (ja) * 2020-04-06 2021-10-14 三菱重工業株式会社 固体炭素生成装置および固体炭素生成方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4328341A3 (en) * 2020-09-25 2024-07-17 Carbon Technology Holdings, LLC Bio-reduction of metal ores integrated with biomass pyrolysis

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56123332A (en) * 1980-03-01 1981-09-28 Kobe Steel Ltd Calcining method for iron ore pellet
JP2021165214A (ja) * 2020-04-06 2021-10-14 三菱重工業株式会社 固体炭素生成装置および固体炭素生成方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
See also references of EP4575020A4
VOLODYMYR SHATOKHA: "Iron Ores and Iron Oxide Materials", INTECHOPEN, 11 July 2018 (2018-07-11), pages 41 - 59

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EP4575020A1 (en) 2025-06-25
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EP4575020A4 (en) 2025-07-09
JPWO2024070135A1 (enrdf_load_stackoverflow) 2024-04-04

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