WO2025115363A1 - コークスの製造方法 - Google Patents

コークスの製造方法 Download PDF

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Publication number
WO2025115363A1
WO2025115363A1 PCT/JP2024/034003 JP2024034003W WO2025115363A1 WO 2025115363 A1 WO2025115363 A1 WO 2025115363A1 JP 2024034003 W JP2024034003 W JP 2024034003W WO 2025115363 A1 WO2025115363 A1 WO 2025115363A1
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WIPO (PCT)
Prior art keywords
mass
carbonaceous material
coke
coal
biomass
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PCT/JP2024/034003
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English (en)
French (fr)
Japanese (ja)
Inventor
佑哉 河合
勇介 土肥
貴 松井
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JFE Steel Corp
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JFE Steel Corp
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Priority to JP2024571978A priority Critical patent/JPWO2025115363A1/ja
Publication of WO2025115363A1 publication Critical patent/WO2025115363A1/ja
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    • 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
    • C10B53/02—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of cellulose-containing material
    • 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
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel

Definitions

  • the present invention relates to a method for producing coke, and in particular, to a method for producing coke that can produce high-strength coke when producing coke using biomass raw materials.
  • the lump coke used in blast furnaces is produced by carbonizing coal in a carbonization furnace, which causes the coal to soften and melt, bonding together. Therefore, caking coal, which has excellent softening and melting properties, is used to produce high-strength coke.
  • biomass-derived raw materials do not soften and melt like coal, so when used in the conventional process of producing coke from coal, they produce low-strength coke with many defects. Therefore, when using biomass-derived raw materials, it is necessary to devise ways to prevent a decrease in coke strength.
  • Non-Patent Document 2 describes a method for improving the bulk density of coal based on a preheated coal charging method in which coal is preheated and dried at a high temperature of about 200°C before being charged.
  • Patent Documents 1 and 2 also describe a method of improving the bulk density of coal by adding a bulk density improver to a coal blend.
  • Non-Patent Document 2 the coal is preheated and dried at a high temperature of about 200°C before being charged, so a nitrogen atmosphere is required to prevent ignition and oxidation of the coal. This requires additional equipment to maintain the nitrogen atmosphere, and if the nitrogen atmosphere is not maintained, there is a risk of explosion or ignition due to high-temperature, low-moisture coal.
  • the bulk density is improved by using additives that are generally known to be effective in improving slipperiness.
  • additives that are generally known to be effective in improving slipperiness.
  • raw materials other than those used in normal coke production are added, which may reduce the coke quality, such as coke strength, and also poses the problem of increased costs due to the addition of expensive chemicals.
  • the present invention was made in consideration of the above problems, and its purpose is to provide a coke manufacturing method that does not require operations that pose a risk of fire and that can produce high-strength coke even when using raw materials derived from biomass.
  • the inventors conducted extensive research to solve the above problems and obtained the following findings. That is, they discovered that by blending fine carbonized biomass with carbonaceous material of the crushed particle size used in normal coke production, the fine carbonized biomass functions as a lubricant between the carbonaceous material particles, improving the slipperiness of the carbonaceous material and increasing the bulk density when the blended coal is charged into a coke oven. They also discovered that by increasing the bulk density when the blended coal is charged, it is possible to obtain coke with strength equal to or greater than that obtained when no biomass-derived raw materials are blended, despite the incorporation of biomass-derived raw materials.
  • the gist of the present invention which was completed based on the above findings, is as follows:
  • a method for producing coke by charging blended coal into a coke oven and carbonizing it comprising the steps of: A method for producing coke, comprising blending carbonaceous material A having a particle size ratio of 3 mm or more of 10 mass % or more and 30 mass % or less, and a particle size ratio of 0.5 mm or more of 60 mass % or more with carbonaceous material B obtained by heat treating biomass having a particle size ratio of 125 ⁇ m or less of 50 mass % or more, in a ratio of 1 mass % or more and 10 mass % or less, to prepare the blended coal.
  • the present invention provides a coke manufacturing method that does not require any operations that pose a risk of fire and that can produce high-strength coke even when using raw materials derived from biomass.
  • FIG. 2 is a cross-sectional view showing a schematic diagram of a bulk density measuring device used in a bulk density measurement test.
  • 11 is a graph showing the relationship between the blending ratio of carbonaceous material B and the strength difference ⁇ DI with respect to a conventional example (No. 1) obtained by dry distilling only carbonaceous material A not containing carbonized biomass.
  • the method for producing coke according to the present invention is a method for producing coke by charging a coal blend into a coke oven and carbonizing it, and is characterized in that a coal blend is prepared by blending carbon material A, which has a ratio of particles of 3 mm or more of 10% by mass to 30% by mass to particles of 0.5 mm or more of 60% by mass to carbon material B obtained by heat treating biomass, which has a ratio of particles of 125 ⁇ m or less of 50% by mass to particles of 125 ⁇ m or less, in a ratio of 1% by mass to 10% by mass.
  • the inventors believed that if the bulk density could be improved by appropriately controlling the particle size distribution of the coal blend charged into the coke oven, it would be possible to suppress the decline in coke strength that is a concern when using raw materials derived from biomass.
  • the finely powdered carbonized biomass acts as a bulk density improver, making it possible to improve the bulk density of the coal blend charged into the coke oven.
  • the coke manufacturing method of the present invention is a technology that improves the bulk density of the blended coal when it is charged by blending finely powdered carbonaceous material (carbonaceous material B) with the blended coal (carbonaceous material A) used in normal coke manufacturing.
  • the blended coal (carbonaceous material A) used in normal coke manufacturing is mainly composed of carbonaceous materials such as coal, pitches, oil coke, and coal dry distillate.
  • a coal blend is prepared by mixing carbonaceous material A, which has a particle size of 3 mm or more at 10% to 30% by mass and a particle size of 0.5 mm or more at 60% by mass, with fine carbonaceous material B, which has a particle size of 125 ⁇ m or less at 50% by mass, in a ratio of 1% to 10% by mass.
  • the carbonaceous material A which has a ratio of particles of 3 mm or more of 10% by mass to 30% by mass to 60% by mass to particles of 0.5 mm or more, is the particle size used in normal coke production. Conventional knowledge has it that reducing the particle size of the coal blend reduces the bulk density of the coal blend charged into the coke oven. Therefore, in the present invention, the crushed particle size of the carbonaceous material A, which accounts for the majority of the coal blend, is controlled so that the ratio of particles of 3 mm or more is 10% by mass to 30% by mass.
  • the particle size of carbonaceous material A is controlled so that the proportion of particles of 3 mm or more is 30 mass% or less.
  • the particle size of carbonaceous material A is controlled so that the proportion of particles of 3 mm or more is 10 mass% or more.
  • the proportion of particles of 3 mm or more in the particle size of carbonaceous material A is 15 mass% or more and 25 mass% or less.
  • the particle size of carbonaceous material A there is no particular upper limit to the particle size of carbonaceous material A as long as the proportion of particles of 3 mm or more in the particle size of carbonaceous material A is 30 mass% or less, but from the viewpoint of preventing bias in the components, it is preferable to set it to 25 mm or less.
  • the particle size of carbonaceous material A is set to 60 mass% or more of 0.5 mm or more.
  • the proportion of particle sizes of 0.5 mm or more and less than 3 mm is set to 30 mass% or more and 90 mass% or less.
  • the proportion of particle sizes of 0.5 mm or more of carbonaceous material A is 80 mass% or less.
  • the proportion of fine particles of carbonaceous material A with a particle size of less than 0.5 mm is less than 40 mass%, and preferably less than 20 mass%. If there are many fine particles less than 0.5 mm during crushing, they can be removed by sieving, etc.
  • carbonaceous material B which has a ratio of 125 ⁇ m or less to 50% by mass or more, is a carbonaceous material obtained by heat treating biomass, and is blended in a ratio of 1% by mass to 10% by mass or less with respect to the entire blended coal.
  • carbonaceous material B which has an extremely low particle size relative to carbonaceous material A
  • the bulk density can be improved. Specifically, when the blended coal is charged into a coke oven, fine carbonaceous material B enters between the coarse carbonaceous material A and functions as a lubricant, improving the slipperiness of the blended coal and improving the bulk density.
  • fine carbonaceous material B enters between the coarse carbonaceous material A and breaks the water bridges between the carbonaceous material particles of the blended coal, thereby improving the slipperiness of the carbonaceous material.
  • the blending ratio of carbonaceous material B is preferably 1% by mass to 9% by mass, and more preferably 2% by mass to 5% by mass.
  • biomass is a general term for a certain amount of accumulated animal and plant resources and waste materials originating from these (excluding fossil resources).
  • the biomass used in the carbonaceous material B of the present invention includes all biomass that produces charcoal when pyrolyzed, such as agricultural, forestry, livestock, fisheries, and waste materials.
  • the biomass used as the raw material for carbonized biomass preferably includes biomass with a high effective calorific value, for example, wood-based biomass.
  • Wood-based biomass includes papermaking by-products such as black pulp liquor and chip dust, lumbering by-products such as bark and waste wood, forest residues such as branches, leaves, treetops and short pieces of timber, thinning materials from cedar, cypress and pine species, waste logs from edible fungi and other special forest products, forestry biomass such as firewood and charcoal forests such as chinquapin, oak and pine, and short-rotation forestry biomass such as willow, poplar, eucalyptus and pine. Wood-based biomass also includes general waste such as pruned branches from city and town roadside trees and private garden trees, pruned branches from national and prefectural roadside trees and corporate garden trees, and industrial waste such as construction and building waste.
  • wood-based biomass also includes general waste such as pruned branches from city and town roadside trees and private garden trees, pruned branches from national and prefectural roadside trees and corporate garden trees, and industrial waste such as construction and building waste.
  • agricultural biomass such as rice husks, wheat straw, rice straw, sugarcane residue, palm oil, etc., which are classified as agricultural biomass and are generated from waste and by-products, and rice bran, rapeseed, soybeans, etc., which are generated from energy crops, can also be suitably used as woody biomass.
  • the volatile content of carbonaceous material B is preferably 2% by mass or more and 50% by mass or less. If the volatile content exceeds 50% by mass, the biomass is not carbonized to a sufficient extent, resulting in poor grindability and reduced productivity of carbonaceous material B, which is a fine powder, and this is not preferred. On the other hand, if the volatile content is less than 2% by mass, the coke strength decreases more significantly with the addition of carbonaceous material B than when the volatile content is 2% by mass or more, and it may not be possible to increase the blending ratio of carbonaceous material B.
  • the volatile content of carbonaceous material B is more preferably 4% by mass or more and 45% by mass or less, and even more preferably 6% by mass or more and 30% by mass or less.
  • carbon material B The lower the volatile content of carbon material B, the greater the effect of improving the bulk density of the blended coal by blending it with carbon material B.
  • a low volatile content in carbon material B means that the carbonization of the biomass through heat treatment has progressed further, and carbon material B has become hydrophobic. It is believed that the more hydrophobic carbon material B is, the greater the effect of breaking down the bridges between particles caused by the water in the blended coal, and therefore the greater the effect of improving the slipperiness of the carbon material.
  • the volatile matter content is a value measured according to "Coals and cokes - Industrial analysis methods" (JIS M 8812:2004) as specified in the Japanese Industrial Standards (JIS).
  • the heat treatment of the biomass that is the raw material for carbon material B is preferably carried out in an atmosphere where the supply of oxygen is blocked.
  • it is preferably carried out while the raw biomass is housed in a container that prevents the inflow of air and forms a space through which an inert gas flows (i.e., in a non-oxidizing atmosphere).
  • the heat treatment of the raw biomass can be carried out by heating the container that holds the raw biomass and by heat transfer from the container.
  • the heat treatment time is preferably 1 minute or more, and more preferably 10 minutes or more. This eliminates the temperature difference between the raw biomass and the container, and the entire raw biomass can be uniformly heat-treated. In addition, it is possible to perform heat treatment by reliably raising the temperature of the entire raw carbon material to the heat treatment temperature (i.e., by heating it evenly), and the quality variation of the heat-treated carbon material and the carbon powder can be suppressed.
  • the heat treatment time is sufficient for 60 minutes or less.
  • the heat treatment time refers to the time during which the temperature of the raw biomass reaches a predetermined heat treatment temperature and is maintained at this heat treatment temperature.
  • Heat treatment can be carried out using a heating device such as a rotary kiln, a fluidized bed heating furnace, an electric furnace, a screw type heating furnace, a shaft furnace, or a carbonization furnace.
  • a heating device such as a rotary kiln, a fluidized bed heating furnace, an electric furnace, a screw type heating furnace, a shaft furnace, or a carbonization furnace.
  • the method for adjusting the particle size of carbonaceous material B is not particularly specified as long as the desired particle size is obtained, but in order to finely pulverize the large amounts of carbonaceous material used in coke production, equipment such as a roller mill or tower mill can be used.
  • the moisture content of the coal blend in the present invention is preferably 6% by mass or more and 9% by mass or less. If the moisture content of the coal blend is less than 6% by mass, the drying of the coal blend may increase the risk of fire and may also increase the amount of dust generated. On the other hand, if the moisture content of the coal blend is higher than 9% by mass, the increase in water may reduce the effect of improving bulk density by blending fine carbonaceous material B, and a large amount of heat is required to evaporate the water during carbonization in coke production, which is undesirable.
  • Table 1 shows the particle size of coal A, the particle size and blending ratio of coal B in the coal blend used in the bulk density measurement test, and the moisture content of the coal blend.
  • FIG. 1 is a cross-sectional view showing a schematic diagram of the bulk density measuring device used in the bulk density measurement test.
  • the bulk density measuring device 1 includes a sample hopper 2, a guide 3 installed at the bottom of the sample hopper, and a box-shaped container 4.
  • the guide 3 has an inlet diameter of 300 mm and an outlet diameter of 150 mm.
  • the container 4 is a rectangular box-shaped container with a width of 250 mm, a length of 250 mm (depth direction in Figure 1), and a height of 200 mm, and only the top surface is an opening.
  • a slide gate 5 is installed at the bottom of the sample hopper 2, and by opening the slide gate 5, the blended coal in the hopper 2 falls into the container 4 via the guide 3.
  • the height from the slide gate 5 installed at the bottom of the hopper 2 to the bottom of the container 4 is 2 m.
  • the bulk density of the various coal blends listed in Table 1 was measured using the bulk density measuring device described above. The procedure for measuring bulk density is described below.
  • coal blend carbonaceous material A and carbonaceous material B, which had been prepared to have the particle sizes shown in Table 1, were blended, and water was added and mixed to obtain the moisture content shown in Table 1 to prepare a coal blend.
  • 32 kg of the coal blend was loaded into hopper 2, and then slide gate 5 was opened to drop the coal blend into container 4. After the coal blend had fallen, the coal blend that had protruded to the top of container 4 was removed, and the mass of the coal blend loaded into the container was measured. After that, the weighed coal blend was divided into smaller portions to measure the moisture content, and the bulk density (dry basis, d.b.) of the coal blend was calculated using the following formula (1). The measurement of the coal loading bulk density was performed twice for each level, and the average of the two measurements was used as the bulk density for each level.
  • Table 1 shows the results of measuring the bulk density of each coal blend.
  • levels 1 to 5 which are conventional examples that do not contain fine carbonaceous material B
  • the bulk density decreases as the mass ratio of particles less than 3 mm increases, and as conventional knowledge, the bulk density decreases as the crushing particle size decreases.
  • levels 6 to 26 which are invention examples in which fine carbonaceous material B is blended with carbonaceous material A
  • the bulk density is improved compared to the conventional example in which carbonaceous material B is not blended.
  • level 27 which is a comparative example in which the blending ratio of carbonaceous material B exceeds 10 mass%
  • the bulk density is lower than the conventional example (level 3) in which carbonaceous material B is not blended.
  • a carbonization test was conducted to examine the effect of the blending of fine carbonized biomass on improving bulk density and its effect on coke strength.
  • a blend of coal A which has a vitrinite average maximum reflectance (Ro(-)) of 1.0% and a common logarithm (logMF) of the maximum flowability (MF [ddpm]) of the Gieseler Plastometer of 2.50, was blended with fine carbonized biomass carbon B to produce coke using the following method, and the coke strength was evaluated.
  • the blended coal A and carbonaceous material B which were prepared to have the particle size shown in Table 2, were blended in the blending ratio shown in Table 2, and then water was added and mixed to make the moisture content 7%, to prepare a blended coal for carbonization.
  • 16.5 kg of this blended coal was filled into a carbonization can with the bulk density shown in Table 2, and carbonized in an electric furnace. After carbonization for 6 hours at a furnace wall temperature of 1050°C, it was cooled under a nitrogen atmosphere, and the drum strength was measured using the obtained coke.
  • the drum strength DI_150/15 index was measured in accordance with the rotational strength test method of JIS K2151.
  • level 1 is a conventional example in which carbonaceous material B is not blended
  • levels 2 to 18 are invention examples in which carbonaceous material B is blended
  • level 19 is a comparative example in which the blending ratio of carbonaceous material B is outside the range of the present invention.
  • the bulk density at the time of carbonization for each level reflects the bulk density measurement results in Table 1.
  • ⁇ DI exceeds 0, indicating that the blending of carbonaceous material B has the effect of improving coke strength.
  • level 19 in which the blending ratio of carbonaceous material B is outside the range of the present invention, ⁇ DI is less than 0, and strength is reduced.
  • Figure 2 shows the relationship between the blending ratio of carbonaceous material B and ⁇ DI for level 1, which contains no added carbonaceous material B, and levels 3 to 5, 9, 10, and 19, which contain cedar (100% by mass of particles 106 ⁇ m or less) heat-treated at 500°C as carbonaceous material B, among the examples listed in Table 2.
  • the blending ratio of carbonaceous material B is in the range of 1% by mass or more and 10% by mass or less, an improvement in bulk density is obtained, and ⁇ DI exceeds 0.
  • the present invention provides a technology that can produce high-strength coke without the need for operations that pose a risk of fire, even when using raw materials derived from biomass.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Coke Industry (AREA)
PCT/JP2024/034003 2023-11-29 2024-09-24 コークスの製造方法 Pending WO2025115363A1 (ja)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04106193A (ja) * 1990-08-25 1992-04-08 Mitsubishi Kasei Corp コークス製造用原料炭の粒度管理方法
JP2004307683A (ja) * 2003-04-08 2004-11-04 Kansai Coke & Chem Co Ltd コークスの製造方法
JP2005272569A (ja) * 2004-03-24 2005-10-06 Nippon Steel Corp 木質系バイオマスを用いた高炉用コークスの製造方法
JP2014077086A (ja) * 2012-10-11 2014-05-01 Nippon Steel & Sumitomo Metal 高炉用高反応性コークスの製造方法
JP2014214268A (ja) * 2013-04-26 2014-11-17 新日鐵住金株式会社 高炉用高強度コークスの製造方法
CN113174272A (zh) * 2021-04-07 2021-07-27 徐州工业职业技术学院 作为焦炭制备瘦化剂的竹炭粉制备方法及焦炭瘦化工艺

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04106193A (ja) * 1990-08-25 1992-04-08 Mitsubishi Kasei Corp コークス製造用原料炭の粒度管理方法
JP2004307683A (ja) * 2003-04-08 2004-11-04 Kansai Coke & Chem Co Ltd コークスの製造方法
JP2005272569A (ja) * 2004-03-24 2005-10-06 Nippon Steel Corp 木質系バイオマスを用いた高炉用コークスの製造方法
JP2014077086A (ja) * 2012-10-11 2014-05-01 Nippon Steel & Sumitomo Metal 高炉用高反応性コークスの製造方法
JP2014214268A (ja) * 2013-04-26 2014-11-17 新日鐵住金株式会社 高炉用高強度コークスの製造方法
CN113174272A (zh) * 2021-04-07 2021-07-27 徐州工业职业技术学院 作为焦炭制备瘦化剂的竹炭粉制备方法及焦炭瘦化工艺

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