WO2025057472A1 - 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
WO2025057472A1
WO2025057472A1 PCT/JP2024/016348 JP2024016348W WO2025057472A1 WO 2025057472 A1 WO2025057472 A1 WO 2025057472A1 JP 2024016348 W JP2024016348 W JP 2024016348W WO 2025057472 A1 WO2025057472 A1 WO 2025057472A1
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WIPO (PCT)
Prior art keywords
biomass
coke
coal
less
carbonized
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PCT/JP2024/016348
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English (en)
French (fr)
Japanese (ja)
Inventor
佑哉 河合
孝徳 ▲高▼嶋
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JFE Steel Corp
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JFE Steel Corp
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Priority to AU2024339260A priority Critical patent/AU2024339260A1/en
Priority to EP24864981.6A priority patent/EP4737537A1/en
Priority to JP2024553506A priority patent/JP7593537B1/ja
Publication of WO2025057472A1 publication Critical patent/WO2025057472A1/ja
Anticipated expiration legal-status Critical
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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 that uses biomass as part of the raw material.
  • Coke is a carbon-based lump-shaped product obtained by carbonizing coal.
  • Coke used in blast furnaces functions as a heat source and reducing agent, as well as a support material that ensures air circulation and liquid permeability inside the blast furnace. Therefore, lump coke is required to have mechanical strength in order to ensure stable operation of the blast furnace.
  • a coal blend consisting of several types of coal mixed in a specific ratio is used.
  • the coal blend is either directly or molded and then carbonized at a temperature of 1000°C or higher to obtain lump-shaped coke in which the coal is bonded together.
  • caking coal which has the property of easily softening and melting, as part of the coal blend, it is possible to obtain coke with high strength.
  • Ro average maximum reflectance of vitrinite
  • MF maximum fluidity
  • Patent Document 1 describes a method for producing highly reactive coke for blast furnaces in which biomass is heated to at least 1000°C or higher for pyrolysis, and the resulting solid biomass char with a diameter of 1 mm or less is added to blended coal.
  • Ro and MF are effective indicators for managing coke strength, but both are indicators that are based on the assumption that they are measured for coal. For this reason, even if one attempts to measure Ro and MF for a sample consisting only of raw materials derived from biomass, it is either impossible to perform the measurement due to the large difference in properties between coal and biomass, or even if it were possible to measure, the measured value cannot be used as an indicator for managing coke strength. Therefore, a new indicator for managing coke strength is needed.
  • the present invention was made in consideration of the above problems, and its purpose is to present new indicators for biomass-derived raw materials that can replace part of the coal used to produce coke for blast furnaces, and to provide a means for producing high-strength coke even when biomass-derived raw materials are blended with coal.
  • the ratio of the carbonized biomass in the mixture is 1.0% by mass or more and 10.0% by mass or less, A method for producing coke described in [1] or [2] above.
  • the proportion of the blended coal for coke production having a particle size of 3.0 mm or less is 70% by mass or more and 100% by mass or less, A method for producing coke described in any one of [1] to [3] above.
  • the present invention clarifies the properties of biomass-derived raw materials suitable for replacing part of the coal used in the production of coke for blast furnaces. This makes it possible to produce high-strength coke even when biomass-derived raw materials are blended with coal. It also makes it possible to reduce carbon dioxide emissions derived from fossil fuels.
  • 1 is a graph showing the relationship between the shrinkage rate of carbonized biomass and the drum strength index of coke using carbonized biomass having a particle size of 3.0 mm or less as part of the raw material. 1 is a graph showing the relationship between the shrinkage rate of carbonized biomass and the drum strength index of coke using carbonized biomass having a particle size of 1.0 mm or less as part of the raw material.
  • the method for producing coke according to the present invention is characterized in that when carbonized biomass having a particle size of 3.0 mm or less is blended in a predetermined ratio with blended coal for coke production and the resulting mixture is carbonized to produce coke, the shrinkage rate of the carbonized biomass at 600°C to 1000°C is 4.0% or more and 10.0% or less.
  • biomass refers to organic industrial resources derived from plants and animals that exist in the current ecosystem.
  • the organic matter that constitutes biomass circulates within the ecosystem while changing its form.
  • the carbon dioxide generated when biomass is burned originates from the carbon that was originally absorbed into the living organisms of plants and animals when they grew, so it does not affect the increase or decrease of the total amount of carbon dioxide in the atmosphere and is considered to be in a so-called carbon neutral state.
  • the carbon dioxide generated when fossil fuels are burned originates from underground resources isolated from the current ecosystem and is therefore not considered to be in a carbon neutral state. Therefore, fossil fuels such as coal and oil are not included in the biomass in this embodiment.
  • the biomass used in this embodiment may be any type of biomass that can be used as an industrial resource among products produced in fields such as agriculture, forestry, livestock farming, and fisheries, and waste generated during the production process, as long as it satisfies the specified conditions described below.
  • the biomass includes at least one of palm kernel shells and woody biomass.
  • Palm kernel shells are biomass produced as a by-product after extracting coconut oil from palm kernels. They are suitable as biomass for use in this embodiment because they are inexpensive and have moderate strength.
  • Examples of woody biomass include biomass made of wood from coniferous trees such as cedar, pine, and cypress, and broad-leaved trees such as zelkova, birch, and eucalyptus. The part of the wood is not limited.
  • Woody biomass also includes unused parts such as waste wood from construction and papermaking, and thinning wood generated in forestry. Sawdust produced during lumber manufacturing is a typical example of woody biomass.
  • the method for producing coke according to the present invention uses carbonized biomass produced by heat-treating biomass.
  • the biomass When heat-treating biomass, the biomass is heat-treated in an air-tight atmosphere.
  • the atmosphere when heat-treating biomass By setting the atmosphere when heat-treating biomass to an air-tight atmosphere, the progress of combustion of the biomass is hindered and the biomass can be carbonized.
  • a container is prepared that prevents air from entering and forms a space through which an inert gas flows, and biomass is loaded into the container and heat-treated.
  • the temperature at which the biomass is heat-treated may be adjusted appropriately depending on the type and particle size of the biomass so that the shrinkage rate at 600°C to 1000°C falls within the appropriate range.
  • a temperature of 400°C or higher will allow sufficient carbonization and improve crushability, while a temperature of 800°C or lower will place the shrinkage rate, described below, in the appropriate range, so a temperature of 400°C or higher and 800°C or lower is preferred.
  • heat treatment temperature refers to the maximum temperature reached by the biomass when heat-treated.
  • the heat treatment time varies depending on the type of biomass and the mass of biomass to be heat treated at one time, but is preferably 1 minute or more and 60 minutes or less. A more preferable lower limit of the heat treatment time is 10 minutes or more. A more preferable upper limit of the heat treatment time is 30 minutes or less.
  • heat treatment time refers to the time from when the temperature of the biomass during heat treatment reaches the temperature at which heat treatment is performed until the heat treatment temperature is stopped being maintained.
  • the proportion of the carbonized biomass having a particle size of 3.0 mm or less is 70% by mass or more and 100% by mass or less. If the proportion of the particle size of 3.0 mm or less is 70% by mass or more and 100% by mass or less, the carbonized biomass can be homogeneously mixed with the blended coal.
  • a preferred particle size range of the carbonized biomass is 100% by mass of a particle size of 3.0 mm or less. There is no lower limit for the particle size. In other words, the particle size may be larger than 0 (zero).
  • a known pulverizer can be used. The pulverization may be performed on the biomass before carbonization, on the carbonized biomass after carbonization, or on both.
  • powder size corresponds to the nominal mesh size of a test sieve as specified in Japanese Industrial Standards Z 8801-1:2019 "Test sieves - Part 1: Metal mesh sieves.”
  • powders and granular materials with a particle size larger than X mm are powders and granular materials that remain on a sieve with a nominal mesh size of X mm when sieved through a sieve.
  • Powders and granular materials with a particle size of Y mm or less are powders and granular materials that fall through a sieve with a nominal mesh size of Y mm when sieved through a sieve.
  • the yield can be increased and production costs can be reduced by omitting classification using sieves.
  • the proportion of particle sizes of 3.0 mm or less in the particle size distribution of the carbonized biomass based on mass is 70 mass% or more.
  • the proportion of particle sizes of 3.0 mm or less is preferably 80 mass% or more, and more preferably 90 mass% or more.
  • the upper limit of the proportion of particle sizes of 3.0 mm or less is 100 mass%.
  • the particle size distribution of the carbonized biomass based on mass can be determined by known methods, such as a method of measuring the weight of a sample sieved using multiple sieves with different mesh sizes from a sample taken from the large amount of carbonized biomass produced, or a method of irradiating a sample with a laser.
  • coke is produced by carbonizing a mixture obtained by blending a coal blend for coke production with carbonized biomass in a predetermined ratio.
  • the coal blend may be any coal blend suitable for coke production.
  • a coal blend suitable for coke production refers to a coal blend that can produce high-strength coke by carbonizing only the coal blend as a raw material. Whether a coal blend is suitable for coke production or not can be predicted from the Ro and MF values of the coal blend.
  • the proportion of coal particles with a particle size of 3.0 mm or less in the coal blend for coke production is preferably 70% by mass or more and 100% by mass or less. If the coal blend has a coarse particle size, a distribution of properties will occur in the production of coke using a mixture of coal components with different properties. Therefore, it is preferable that the proportion of coal particles with a particle size of 3.0 mm or less in the coal blend is 70% by mass or more. More preferably, the proportion of coal particles with a particle size of 3.0 mm or less is 75% by mass or more.
  • the proportion of coal particles with a particle size of 3.0 mm or less is preferably 90% by mass or less, and more preferably 85% by mass or less.
  • the proportion of carbonized biomass in the mixture obtained by blending carbonized biomass in a specified ratio with blended coal for coke production is 1.0 mass% or more, a significant effect in reducing carbon dioxide emissions is obtained, and when it is 10.0 mass% or less, the strength of the obtained coke is not significantly reduced, so it is preferable that the proportion of carbonized biomass is 1.0 mass% or more and 10.0 mass% or less.
  • a more preferable proportion of biomass is 2.0 mass% or more and 7.0 mass% or less.
  • the mixture obtained by blending blended coal and carbonized biomass in a predetermined ratio may be sufficiently mixed without performing any special operation specialized for mixing.
  • Specific examples of such cases include when the mixture transported by a belt conveyer falls onto the next belt conveyer, when blended coal and carbonized biomass are blended and then pulverized using pulverizing equipment, and when blended coal and carbonized biomass are blended and then the moisture content is adjusted while stirring using coal moisture control equipment. In such cases, the equipment and costs required for mixing can be reduced, which is preferable.
  • the blended coal and carbonized biomass are mixed uniformly. This can prevent the problem of the carbonized biomass, which does not soften or melt when heated, being unevenly distributed in one place and remaining unsolidified even after the carbonization process.
  • a coal mixer can be used to mix the blended coal and carbonized biomass.
  • a coal mixer for example, a mixer that mainly performs convection mixing, a mixer that mainly performs shear mixing, or a mixer that performs a combination of convection mixing and shear mixing can be used.
  • convection mixing is mixing that mainly involves convection and diffusion of the sample
  • shear mixing is mixing that involves shearing, collision, grinding, etc. of the sample.
  • a mixture obtained by blending a carbonized biomass with a blended coal for coke production in a predetermined ratio is carbonized to produce coke.
  • the mixture is charged into a coke oven and carbonized by heating in an air-tight atmosphere.
  • the carbonization temperature is 900°C or higher, coke of sufficient strength will be obtained. 950°C or higher is preferable.
  • the carbonization temperature is preferably 1250°C or lower, and more preferably 1100°C or lower.
  • the carbonization temperature refers to the maximum temperature reached by the mixture during carbonization.
  • the coke manufacturing method according to this embodiment is characterized in that the contraction rate of the carbonized biomass at 600°C to 1000°C is 4.0% or more and 10.0% or less.
  • Samples for shrinkage rate measurement can be prepared by crushing carbonized biomass and molding it to dimensions that fit the specifications of the measurement device. It is preferable to set the crushed particle size of the carbonized biomass to 1/10 or less of the height of the sample for shrinkage rate measurement, i.e., the length measured in the direction in which the amount of shrinkage is measured, since this eliminates the effects of anisotropy in the amount of shrinkage of the carbonized biomass sample and allows for stable measurement results. From this perspective, it is preferable for the crushed particle size of the carbonized biomass to be, for example, 0.3 mm or less, and more preferably 0.1 mm or less.
  • the sample for shrinkage rate measurement after molding is required to have few voids. Therefore, although it depends on the density of the carbonized biomass itself used in the test, the density of the sample for shrinkage rate measurement is preferably 0.2 g/ cm3 or more, and more preferably 0.4 g/ cm3 .
  • the sample may be filled into a container whose dimensions match the specifications of the measuring device and used as the sample for measuring the amount of shrinkage.
  • the container in order to eliminate the effects of thermal expansion of the container, it is preferable that the container be made of a material with a small thermal expansion coefficient, such as alumina.
  • a known measuring device such as a Thermomechanical Analyzer (TMA) or a thermal dilatometer can be used.
  • TMA Thermomechanical Analyzer
  • the measuring device used to measure the shrinkage rate must be capable of heating the sample up to 1000°C while controlling the temperature, and of measuring the change in length of the sample in the direction in which the shrinkage rate is being measured. It is also preferable that the measuring device is equipped with a mechanism such as a contactor that can detect the change in dimension when the sample shrinks.
  • the shrinkage rate of the sample is measured in a temperature range from 600°C to 1000°C.
  • biomass releases moisture and volatile matter as the temperature rises, which causes shrinkage.
  • caking coal which is widely used in coke production
  • complex changes not seen in biomass occur as the temperature rises. That is, caking coal softens and melts at temperatures of 300°C or higher, and the caking coal pieces bond together. It then resolidifies at temperatures of 500°C or higher, and the entire coal becomes solid. After resolidification, it further shrinks while releasing volatile matter in a temperature range of 1000°C.
  • the shrinkage rate of the carbonized biomass is measured in a temperature range of 600°C or higher after the softening and melting of the caking coal is completed and resolidification occurs. This makes it possible to directly compare the shrinkage rate of caking coal that softens and melts with the shrinkage rate of carbonized biomass that does not soften and melt.
  • the upper limit of the temperature range for measuring the shrinkage rate of the sample is set to 1000°C.
  • Carbonized biomass that satisfies the range of shrinkage rates specified in this embodiment has a shrinkage rate close to that of blended coal. For this reason, it is believed that stress generation and accumulation of strain due to differences in the amount of shrinkage are unlikely to occur, and that a decrease in strength is unlikely to occur.
  • the shrinkage rate at 600°C to 1000°C measured using samples for shrinkage rate measurement can be controlled by the type of biomass and the conditions of heat treatment during carbonization. The higher the heat treatment temperature, the lower the shrinkage rate.
  • the conditions of heat treatment to achieve a shrinkage rate of 4.0% or more and 10.0% or less vary depending on the type of biomass used and can be adjusted appropriately, but in most cases the shrinkage rate can be adjusted to 4.0% or more by performing heat treatment at a temperature generally below 700°C.
  • the rate of temperature rise in measuring the contraction rate of the sample is preferably 1°C or more per minute, as this does not take too long to measure. Also, since the rate of temperature rise of coal in normal coke production is slow, it is preferable that the rate of temperature rise be 10°C or less per minute. Therefore, it is preferable that the rate of temperature rise in measuring the contraction rate of the sample is 1°C or more and 10°C or less per minute. A more preferable lower limit of the rate of temperature rise is 2°C or more per minute. A more preferable upper limit of the rate of temperature rise is 5°C or less per minute.
  • the atmosphere in which the shrinkage rate of the sample is measured is preferably an air-tight atmosphere, for example, an atmosphere in which an inert gas is circulating.
  • the method for producing coke according to the present invention is characterized in that when carbonized biomass having a particle size of 1.0 mm or less is blended in a predetermined ratio with blended coal for coke production and the resulting mixture is carbonized, the shrinkage rate of the carbonized biomass at 600°C to 1000°C is 2.0% or more and 10.0% or less.
  • the range of the shrinkage rate of the carbonized biomass to which the present invention can be applied can be expanded to a range lower than 4.0%.
  • the particle size of the carbonized biomass is 1.0 mm or less
  • carbonized biomass with a shrinkage rate of 2.0% or more and 10.0% or less at 600°C to 1000°C can be used.
  • the effect of the present invention can be confirmed by evaluating the strength of the coke obtained by the coke manufacturing method according to the present embodiment.
  • evaluating the strength of coke There are various methods for evaluating the strength of coke, but among them, the method of evaluating the strength of coke by the rotational strength by the drum method specified in the Japanese Industrial Standards K 2151:2004 "Cokes - Test Methods" is a test that simulates the generation of powder from coke, which is a problem when used in a blast furnace, and is currently the most widely used in Japan, and is therefore preferable.
  • the drum method is a method in which a sample is inserted into a specified drum testing machine, rotated at a specified speed for a specified number of rotations, and then sieved through a specified sieve, the mass of each classification is determined, and the added percentage (%) of the sample is expressed as the drum strength index (symbol: DI).
  • the drum rotation speed was set to 150 rpm, and the ratio of the mass of coke that did not pass through a sieve with a mesh size of 15 mm after rotation to the mass of coke inserted into the drum testing machine was defined as the drum strength index (%).
  • the drum strength index indicates the mass ratio of coke that was not crushed to a size of 15 mm or less even when rotated in the drum testing machine. A higher DI value indicates a higher strength of the coke.
  • a coal blend with Ro of 1.0% and common logarithm of MF (log(MF/ddpm)) of 2.5 was prepared. This coal blend was pulverized to produce a coal blend with a particle size of 3.0 mm or less adjusted to 100% by mass.
  • the shrinkage rate of carbonized biomass was measured using the following method.
  • the carbonized biomass was crushed to 0.1 mm or less, and the crushed sample was filled to a height of 7.0 mm in a cylindrical alumina cell with a diameter of 6.7 mm and a height of 9.2 mm to prepare a sample for shrinkage rate measurement.
  • the sample was set in a thermomechanical analyzer TMA-60 manufactured by Shimadzu Corporation, and the temperature was raised at a rate of 3°C per minute in a nitrogen atmosphere to measure the shrinkage rate in the height direction of the sample in the temperature range from 600°C to 1000°C.
  • the measured values obtained are shown in Table 1.
  • the above measurement results show that the higher the heat treatment temperature of the biomass, the smaller the shrinkage rate.
  • the shrinkage rate of palm kernel shells was 3.3% or less when the heat treatment temperature was 800°C or higher.
  • the shrinkage rate of cedar was 0.8% when the heat treatment temperature was 900°C or higher.
  • the blended coal and biomass were blended so that the blending ratio of the biomass in the mixture was 2.0%, 5.0%, or 8.0%, and the mixture was adjusted to have a moisture content of 8.0 mass%. 16 kg of each level was prepared.
  • the mixture was filled into a stainless steel container, inserted into an electric furnace through which nitrogen gas was circulated, heated, and carbonized.
  • the bulk density of the mixture in the container was 775 kg/m 3 on an anhydrous basis.
  • the container filled with the mixture was charged into an electric furnace set at a furnace wall temperature of 1050° C., and carbonized while maintaining the furnace wall temperature for 6 hours from the charging.
  • the container was then transferred to a cooling facility through which nitrogen gas at room temperature was circulated and cooled to obtain coke containing biomass as a raw material.

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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/JP2024/016348 2023-09-13 2024-04-25 コークスの製造方法 Pending WO2025057472A1 (ja)

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Application Number Priority Date Filing Date Title
AU2024339260A AU2024339260A1 (en) 2023-09-13 2024-04-25 Method of producing coke
EP24864981.6A EP4737537A1 (en) 2023-09-13 2024-04-25 Method for producing coke
JP2024553506A JP7593537B1 (ja) 2023-09-13 2024-04-25 コークスの製造方法

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JP2023148711 2023-09-13
JP2023-148711 2023-09-13

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7852820B1 (ja) 2025-04-22 2026-04-28 Ｊｆｅスチール株式会社 スタンプチャージ式コークス炉用バイオマス炭、スタンプチャージ式コークス炉用バイオマス炭の製造方法、および、コークスの製造方法
JP7852819B1 (ja) 2025-04-15 2026-04-28 Ｊｆｅスチール株式会社 スタンプチャージ式コークス炉用バイオマス炭、スタンプチャージ式コークス炉用バイオマス炭の製造方法、および、コークスの製造方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004277452A (ja) * 2003-03-12 2004-10-07 Nippon Steel Corp 高炉用コークスの製造方法
JP2004307683A (ja) * 2003-04-08 2004-11-04 Kansai Coke & Chem Co Ltd 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

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004277452A (ja) * 2003-03-12 2004-10-07 Nippon Steel Corp 高炉用コークスの製造方法
JP2004307683A (ja) * 2003-04-08 2004-11-04 Kansai Coke & Chem Co Ltd 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

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7852819B1 (ja) 2025-04-15 2026-04-28 Ｊｆｅスチール株式会社 スタンプチャージ式コークス炉用バイオマス炭、スタンプチャージ式コークス炉用バイオマス炭の製造方法、および、コークスの製造方法
JP7852820B1 (ja) 2025-04-22 2026-04-28 Ｊｆｅスチール株式会社 スタンプチャージ式コークス炉用バイオマス炭、スタンプチャージ式コークス炉用バイオマス炭の製造方法、および、コークスの製造方法

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