EP2543716B1 - Procédé de production de ferrocoke pour la métallurgie - Google Patents

Procédé de production de ferrocoke pour la métallurgie Download PDF

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Publication number
EP2543716B1
EP2543716B1 EP11750576.8A EP11750576A EP2543716B1 EP 2543716 B1 EP2543716 B1 EP 2543716B1 EP 11750576 A EP11750576 A EP 11750576A EP 2543716 B1 EP2543716 B1 EP 2543716B1
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EP
European Patent Office
Prior art keywords
ferrocoke
briquette
temperature
carbonization
coke
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.)
Active
Application number
EP11750576.8A
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German (de)
English (en)
Other versions
EP2543716A4 (fr
EP2543716A1 (fr
Inventor
Takeshi Sato
Hiroyuki Sumi
Hidekazu Fujimoto
Takashi Anyashiki
Hideaki Sato
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.)
JFE Steel Corp
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JFE Steel Corp
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Publication date
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Publication of EP2543716A1 publication Critical patent/EP2543716A1/fr
Publication of EP2543716A4 publication Critical patent/EP2543716A4/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • C10B53/08—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form in the form of briquettes, lumps and the like
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
    • C10B57/04—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
    • C10B57/04—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition
    • C10B57/06—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition containing additives
    • 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
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B5/00—Making pig-iron in the blast furnace
    • C21B5/007—Conditions of the cokes or characterised by the cokes used
    • 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 metallurgical ferrocoke manufacturing method of manufacturing ferrocoke by briquetting a carbonaceous material and iron ore and carbonizing the briquette.
  • Non-Patent Literature 1 To decrease a reducing agent ratio in a blast furnace, it is effective to decrease a thermal reserve zone temperature generated in the blast furnace (for example, see Non-Patent Literature 1).
  • An example of a method of decreasing the thermal reserve zone temperature is a method of decreasing a starting temperature of a gasification reaction (endothermic reaction) of coke expressed by equation (1) below.
  • Ferrocoke manufactured by carbonization of a briquette obtained by mixing and briquetting a carbonaceous material (coal) and iron ore is able to increase CO 2 reactivity of coke in ferrocoke due to a catalytic effect of reduced iron ore, and to decrease a reducing agent ratio due to a decrease in a thermal reserve zone temperature following the increase in the CO 2 reactivity (for example, refer to Patent Literature 1).
  • Patent Literature 1 Japanese Laid-open Patent Publication No. 2006-28594
  • the invention has been made in view of the above problems, and its object is to provide a metallurgical ferrocoke manufacturing method by which, when manufacturing ferrocoke by carbonizing a mixture of a carbonaceous material and iron ore, CO 2 reactivity of coke in ferrocoke inside a blast furnace is increased, thereby enabling a decrease in a thermal reserve zone temperature and a decrease in a reducing agent ratio.
  • the present invention is a metallurgical ferrocoke manufacturing method of manufacturing ferrocoke by briquetting a mixture of a carbonaceous material and iron ore to form a briquette and carbonizing the briquette, and is characterized in that a maximum temperature of ferrocoke during the carbonization is in a range of 800°C or higher and 900°C or lower.
  • the maximum temperature of the ferrocoke during the carbonization is preferably in a range of 800°C or higher and 850°C or lower.
  • the particle diameter of the ferrocoke is in a range of 15 mm or greater and 28 mm or less.
  • the ferrocoke preferably has an iron content in a range of 5 mass% or greater and 40 mass% or less and more preferably in a range of 10 mass% or greater and 40 mass% or less.
  • the carbonization of the briquette is performed in a vertical furnace and a furnace top gas of the vertical furnace is used as a gas that heats up the briquette.
  • the furnace top gas includes carbon monoxide, carbon dioxide, hydrogen, methane, and nitrogen.
  • the gas that heats up the briquette desirably includes at least two components selected from a group consisting of carbon monoxide, carbon dioxide, hydrogen, methane, and nitrogen.
  • ferrocoke having high CO 2 reactivity in a blast furnace is able to be manufactured, and a reducing agent ratio in the blast furnace is able to be decreased due to a decrease in a thermal reserve zone temperature. Further, according to the preset invention, a carbonization temperature is not increased by what is more than necessary when ferrocoke is manufactured, and thus contribution to adjustment of a necessary amount of heat is achievable.
  • ferrocoke used in blast furnace operations which is manufactured by carbonizing a briquette obtained by briquetting a mixture of a carbonaceous material and iron ore
  • a method of manufacturing ferrocoke was studied in order to increase CO 2 reactivity of coke in ferrocoke, and the following considerations were made.
  • Ferrocoke was manufactured by carbonizing, in a batch-type pressurized carbonization furnace, a briquette (briquette) obtained by briquetting a mixture of coal and iron ore (70 mass% of coal; and 10, 20, 30, and 40 mass% of iron ore) using a briquette machine.
  • a shape of the briquette is illustrated in FIG. 1 .
  • L is 30 mm
  • B is 25 mm
  • T is 18 mm.
  • L represents the length
  • B represents the breadth
  • T represents the thickness
  • a representative particle diameter of ferrocoke is represented by (length ⁇ breadth ⁇ thickness) 1/3 , that is, (L ⁇ B ⁇ T) 1/3 .
  • ferrocoke carbonization temperatures were 800°C, 850°C and 900°C.
  • a ferrocoke carbonization temperature is the maximum temperature during the carbonization, and is obtained by measuring a temperature at a central portion of the briquette. Temperature was increased up to this maximum temperature at 5°C/min, and maintained at the maximum temperature for 90 minutes.
  • An atmosphere was a mixed gas of 30% of hydrogen, 11% of carbon monoxide, 17% of carbon dioxide, 21% of nitrogen, 5% of water vapor, and 16% of methane (each in vol%).
  • the temperature within the briquette is desirably maintained homogeneously.
  • a vertical carbonization furnace which is a gas and solid temperature countercurrent moving bed, it is necessary to set operating conditions so as to secure a time for the temperature within the briquette to become homogeneous.
  • FIG. 3 illustrates results of measurement of time difference between a time at which a surface layer reaches 850°C and a time at which the center reaches 850°C when the temperature was increased from 25°C to 850°C at 5°C/min as the volume of the briquette was varied.
  • a briquette volume of 6 cc was used as a reference condition, and sorting was done with relative values with respect to a case of the briquette volume of 6 cc.
  • the atmosphere was a mixed gas of 30% of hydrogen, 11% of carbon monoxide, 17% of carbon dioxide, 21% of nitrogen, 5% of water vapor, and 16% of methane (each in vol%), and the temperatures of the surface layer and the center of the briquette were measured.
  • the time for the entire briquette to reach a homogeneous temperature increases as the volume of the briquette increases.
  • FIG. 4 A relation between the briquette volume and the briquette descending speed necessary for the inside of the briquette to reach a homogeneous temperature when a zone length at 850°C is 1.5 m and the briquette descending speed of 1 m/hour for the briquette volume of 6 cc is used as a reference is illustrated in FIG. 4 . It is necessary to decrease the descending speed as the briquette volume is increased. This means a decrease in the production speed, and, when the volume of 6 cc is set as a reference, the production speed decreases by 5% or more when the volume becomes 14 cc or greater.
  • the representative particle diameter of ferrocoke is expressed by (length ⁇ breadth ⁇ thickness) 1/3 as described above, the representative diameter of the volume of 6 cc is equivalent to 23.8 mm, the representative diameter of the volume of 14 cc is equivalent to 28.3 mm, and the representative diameter of the volume of 18 cc is equivalent to 30.6 mm.
  • a briquette of a smaller size is more advantageous in terms of productivity, but when use in a blast furnace is assumed, a lower limit of size from the viewpoint of gas permeability is desirably specified.
  • Ferrocoke is desirably used by being mixed with an iron material including sintered steel, a pellet, lump ore, or the like.
  • the iron material including the sintered steel, the pellet, the lump ore, or the like will be referred to as ore. Since it is important in terms of operation to maintain the gas permeability of a mixed layer of ore and ferrocoke, the influence of ferrocoke particle diameter on ventilation resistance of the mixed layer of ore and ferrocoke was investigated. A particle size distribution of ore when the ratio of ferrocoke in the ore was 21 vol% (equivalent to a ferrocoke ratio of 35 mass%) is illustrated in FIG. 5 .
  • Equation (2) A change in the ventilation resistance according to the size of ferrocoke mixed in ore was calculated using equation (2) below.
  • ⁇ represents a shape coefficient (assumed to be 0.7)
  • dp represents an average particle diameter of the ore/ferrocoke mixed layer
  • ⁇ represents a porosity of the ore/ferrocoke mixed layer.
  • Permeability index 1 / ⁇ dp 1.3 ⁇ 1 ⁇ ⁇ 1.3 / ⁇ 3
  • the average diameter of the mixed layer was calculated by correcting the particle size distribution illustrated in FIG. 5 according to an assumed ferrocoke size, and the porosity was assumed from the corrected particle size distribution (see Non-Patent Document 3). The results are illustrated in FIG. 6 . It was found that a change in the ventilation resistance is small in a ferrocoke size range of 15 mm to 35 mm. When the size of ferrocoke is below 15 mm, the average diameter of the mixed layer decreases and thus the ventilation resistance increases. The ventilation resistance also increases under a condition in which the size of ferrocoke is large, but this is caused by a decrease in the porosity due to widening of the particle size distribution.
  • the ferrocoke particle diameter is preferably in a range of 15 mm to 35 mm.
  • the particle diameter of ferrocoke is desirably 28.3 mm or less from the viewpoint of securing the productivity and in a range of 15 mm to 35 mm from the viewpoint of the gas permeability upon use in a blast furnace.
  • the particle diameter of ferrocoke is therefore in a range of 15 mm to 28 mm in consideration of both ensuring the productivity and the gas permeability.
  • FIG. 8 A relation between ferrocoke carbonization temperature and reaction rate of carbon in ferrocoke for ferrocoke that has been reacted up to 1200°C under the conditions of FIG. 7 is illustrated in FIG. 8 .
  • Results were obtained, which indicated that the reaction rates at the ferrocoke carbonization temperatures of 750°C and 950°C were at a lower level, and the maximum value was obtained at 850°C.
  • the ferrocoke carbonization temperature was 750°C
  • the reduction rate of iron ore in ferrocoke was as low as 20% as illustrated in FIG. 2 , and it is thus assumed that the reactivity became low because the catalytic effect of reduced iron was small.
  • Reaction starting temperatures in the above tests of ferrocoke manufactured at a carbonization temperature of 850°C with its iron content varied from 0 mass% to 40 mass% are illustrated in FIG. 9 .
  • FIG. 9 As the content of iron in ferrocoke increases, the effects of reactivity being improved and a decrease in the reaction starting temperature are exhibited. A large effect is exhibited from the iron content of 5 mass%, and the effect is saturated at 40 mass% or greater.
  • the iron content in the ferrocoke is preferably in a range of 5 mass% to 40 mass%, and more preferably in a range of 10 mass% to 40 mass%.
  • ferrocoke having a high CO 2 reactivity was able to be manufactured by setting the temperature of ferrocoke upon the carbonization in a range of 800°C to 900°C, desirably in a range of 800°C to 850°C, and particularly desirably around 850°C.
  • the iron content in ferrocoke is preferably in a range of 5 mass% to 40 mass%, and more preferably in a range of 10 mass% to 40 mass%.
  • Coal is preferably used as the carbonaceous material. Other than coal, biomass or the like may be used.
  • a briquette obtained by briquetting a mixture of coal and iron ore (70 mass% of coal and 30 mass% of iron ore) using a briquette machine was continuously carbonized in a gas heating type vertical carbonization furnace.
  • Some of furnace top gas of the carbonization furnace (30 vol% of hydrogen, 11 vol% of carbon monoxide, 17 vol% of carbon dioxide, 21 vol% of nitrogen, 5 vol% of water vapor, and 16 vol% of (methane + ethane)), which has been heated, was used as gas, and the briquette was heated up by forming a countercurrent moving bed with gas elevating in the carbonization furnace and the briquette continuously descending in the furnace.
  • the ferrocoke manufacturing conditions (ferrocoke carbonization temperatures), the reduction rates of iron in the ferrocoke, the operating conditions (the amounts of ferrocoke used, the chamber oven coke ratios, and pulverized coal ratios), and the blast furnace operation results (reducing agent ratios) are illustrated in Table 1, and a relation between the ferrocoke carbonization temperature and the blast furnace reducing agent ratio is illustrated in FIG. 10 .
  • Table 1 the base is a case of an ordinary blast furnace operation of not using ferrocoke, and cases 1 to 5 are cases in which an operation of uniformly mixing ferrocoke in an ore layer and charging it from the blast furnace top was carried out.
  • the reducing agent ratio is able to be decreased by using ferrocoke as compared to the condition (base) under which ferrocoke is not used.
  • the reducing agent ratio was able to be decreased by 30 kg/t or more when the temperature of ferrocoke in the carbonization (the ferrocoke carbonization temperature) was in a range of 800°C to 900°C. This is assumed to be due to interaction between an effect of a function as a catalyst increasing because of the reduction rate of iron in ferrocoke increasing by an increase in the carbonization temperature and an effect of the reactivity of the coke portion decreasing by an increase in the carbonization temperature.
  • the present invention is applicable to a method of manufacturing ferrocoke by briquetting a mixture of a carbonaceous material and iron ore and carbonizing the briquette formed.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Manufacturing & Machinery (AREA)
  • Metallurgy (AREA)
  • Environmental & Geological Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Geology (AREA)
  • Mechanical Engineering (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Coke Industry (AREA)
  • Manufacture Of Iron (AREA)

Claims (4)

  1. Procédé de fabrication de ferrocoke métallurgique consistant à fabriquer du ferrocoke métallurgique par briquetage d'un mélange de matériau charbonneux et de minerai de fer pour former une briquette et carbonisation de la briquette, une température maximale du ferrocoke pendant la carbonisation étant dans une plage de 800 °C ou plus et 900 °C ou moins,
    pour obtenir un diamètre de particule du ferrocoke dans une plage de 15 mm ou plus et 28 mm ou moins.
  2. Procédé de fabrication de ferrocoke métallurgique selon la revendication 1, dans lequel la température maximale du ferrocoke pendant la carbonisation est dans une plage de 800 °C ou plus et 850 °C ou moins.
  3. Procédé de fabrication de ferrocoke métallurgique selon la revendication 1, dans lequel le ferrocoke a une teneur en fer dans une plage de 5 % en masse ou plus et 40 % en masse ou moins.
  4. Procédé de fabrication de ferrocoke métallurgique selon la revendication 1, dans lequel la carbonisation de la briquette est réalisée dans un four vertical et un gaz de haut de four du four vertical est utilisé comme gaz pour chauffer la briquette.
EP11750576.8A 2010-03-03 2011-02-25 Procédé de production de ferrocoke pour la métallurgie Active EP2543716B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2010046061 2010-03-03
PCT/JP2011/054367 WO2011108466A1 (fr) 2010-03-03 2011-02-25 Procédé de production de ferrocoke pour la métallurgie

Publications (3)

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EP2543716A1 EP2543716A1 (fr) 2013-01-09
EP2543716A4 EP2543716A4 (fr) 2016-07-13
EP2543716B1 true EP2543716B1 (fr) 2019-04-03

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EP (1) EP2543716B1 (fr)
JP (1) JP5790028B2 (fr)
KR (1) KR20120123482A (fr)
CN (1) CN102782095B (fr)
WO (1) WO2011108466A1 (fr)

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CN103468841A (zh) * 2013-09-06 2013-12-25 鞍钢股份有限公司 一种高炉喷吹用兰炭及其制造方法
CN103756701B (zh) * 2014-01-21 2015-11-25 河北联合大学 高反应性焦炭及其生产方法
WO2016208435A1 (fr) 2015-06-24 2016-12-29 Ｊｆｅスチール株式会社 Procédé de production de ferro-coke
CN106635067A (zh) * 2016-11-24 2017-05-10 武汉科思瑞迪科技有限公司 一种生产铁焦的竖炉工艺
CN110093467B (zh) * 2019-06-05 2020-07-17 东北大学 一种铁焦的制备方法
KR102289527B1 (ko) * 2019-09-24 2021-08-12 현대제철 주식회사 고로 환원제비 및 co2 발생량 저감 방법
CN110699142B (zh) * 2019-10-10 2021-02-02 中南大学 一种铁矿烧结生物质燃料及其制备方法和应用
CN110699141B (zh) * 2019-10-10 2021-08-20 中南大学 一种链篦机-回转窑喷吹生物质燃料及其制备方法和应用
JP2022187900A (ja) * 2021-06-08 2022-12-20 株式会社神戸製鋼所 銑鉄製造方法及び鉱石原料
CN113416567B (zh) * 2021-07-08 2022-07-15 山西沁新能源集团股份有限公司 一种铁焦的制备方法及铁焦
CN115612762B (zh) * 2021-07-13 2023-11-03 山西沁新能源集团股份有限公司 一种高冷热强度的铁焦及其制备方法
CN115612760B (zh) * 2021-07-13 2023-11-03 山西沁新能源集团股份有限公司 一种低灰分、高强度的铁焦及其制备方法
CN115612761B (zh) * 2021-07-13 2023-11-03 山西沁新能源集团股份有限公司 一种低灰分、高强度的铁焦及其制备方法
KR102567429B1 (ko) * 2021-07-27 2023-08-17 현대제철 주식회사 고로의 장입물 분포 프로파일 제어 방법

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JPH0428810A (ja) * 1990-05-24 1992-01-31 Nippon Steel Corp 溶融還元製鉄法
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JP4487564B2 (ja) * 2002-12-25 2010-06-23 Ｊｆｅスチール株式会社 フェロコークスの製造方法
JP4556525B2 (ja) * 2004-07-16 2010-10-06 Ｊｆｅスチール株式会社 高炉の操業方法
JP5087868B2 (ja) * 2006-07-05 2012-12-05 Ｊｆｅスチール株式会社 フェロコークスの製造方法
CN101910364B (zh) * 2007-12-26 2014-05-14 杰富意钢铁株式会社 铁焦的制造方法
JP5386838B2 (ja) * 2008-03-21 2014-01-15 Ｊｆｅスチール株式会社 冶金用フェロコークス
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Publication number Publication date
JP5790028B2 (ja) 2015-10-07
CN102782095A (zh) 2012-11-14
CN102782095B (zh) 2015-07-01
EP2543716A4 (fr) 2016-07-13
EP2543716A1 (fr) 2013-01-09
WO2011108466A1 (fr) 2011-09-09
KR20120123482A (ko) 2012-11-08
JP2011202159A (ja) 2011-10-13

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