WO2024224682A1 - 炭素塊成化物の製造方法 - Google Patents

炭素塊成化物の製造方法 Download PDF

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WO2024224682A1
WO2024224682A1 PCT/JP2023/045365 JP2023045365W WO2024224682A1 WO 2024224682 A1 WO2024224682 A1 WO 2024224682A1 JP 2023045365 W JP2023045365 W JP 2023045365W WO 2024224682 A1 WO2024224682 A1 WO 2024224682A1
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carbon
powder
carbonaceous
carbonaceous powder
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French (fr)
Japanese (ja)
Inventor
佑哉 河合
勇介 土肥
大輔 井川
彩良 荒川
健太 竹原
孝徳 ▲高▼嶋
哲也 山本
泉 下山
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JFE Steel Corp
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JFE Steel Corp
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Priority to JP2024517576A priority Critical patent/JP7718585B2/ja
Priority to EP23935453.3A priority patent/EP4656617A1/en
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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
    • C10B53/08—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
    • C10B47/00—Destructive distillation of solid carbonaceous materials with indirect heating, e.g. by external combustion
    • C10B47/02—Destructive distillation of solid carbonaceous materials with indirect heating, e.g. by external combustion with stationary charge
    • C10B47/12—Destructive distillation of solid carbonaceous materials with indirect heating, e.g. by external combustion with stationary charge in which the charge is subjected to mechanical pressures during coking
    • 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
    • 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
    • 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
    • C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • C10B53/04—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of powdered coal

Definitions

  • the present invention relates to a method for producing carbon agglomerates such as coke.
  • the conventional method for producing coke involves crushing caking coal (caking coal) into a powder with 70-100 wt% of particles with a diameter of 3 mm or less, and then carbonizing this powder, which causes the particles of the caking coal to soften and melt in the softening temperature range of about 400-500°C, bonding together to produce coke as a carbon agglomerate.
  • Patent Document 1 discloses a method for producing a high-density carbon material.
  • a carbonaceous material raw material consisting of a self-sintering carbonaceous powder is heated to 400 to 600°C under atmospheric pressure, and then the heated carbonaceous material raw material is pressed at a pressure of 50 to 400 kg/ cm2 while being kept in the above temperature range to be molded into a desired shape, and the obtained molded body is fired and graphitized.
  • the self-sintering carbonaceous powder is bulk mesophase, mesocarbon microbeads, and petroleum- or coal-based raw coke.
  • conventional carbon agglomerates are made mainly from coal with caking properties (caking coal), with a binder such as pitch added as necessary, and the particles of the carbon powder are bonded or fused together to form agglomerates using liquid phase components such as caking coal and binder.
  • caking coal or pitch is not used, carbon agglomerates cannot be obtained, and even if carbon agglomerates are obtained, there is a problem that they do not have sufficient strength.
  • the coke used in the blast furnace process is required to have high strength among carbon agglomerates. For this reason, conventionally, coal with caking properties (caking coal) has been used as a raw material to manufacture coke for use in blast furnaces.
  • Non-Patent Document 1 discloses the results of a study on coke strength (strength of blast furnace coke) using an indirect tensile strength test method.
  • the present invention aims to provide a method for producing carbon agglomerates that can produce high-strength carbon agglomerates that can withstand use in a blast furnace, even when the amount of raw carbon material with poor softening and melting properties used is increased.
  • the inventors discovered a carbonaceous powder agglomeration technology based on a new mechanism that does not rely on a liquid-phase sintering phenomenon in which liquid-phase components that can become volatile are used to bond or fuse carbonaceous powder particles together. That is, the inventors discovered that by pressurizing a specific carbonaceous powder while heating it at a temperature range of 600°C or higher, the particles of the carbonaceous powder are bonded together by a solid-phase sintering phenomenon, unlike the conventional agglomeration by a liquid-phase sintering phenomenon, and carbon agglomerates can be produced.
  • the specific carbonaceous powder is a fine carbonaceous powder in which the amount of volatile matter is appropriately controlled and the maximum particle size is 300 ⁇ m or less.
  • Conventional agglomeration by a liquid-phase sintering phenomenon occurs when caking coal powder is heated to 400 to 500°C to soften and melt it.
  • the specific carbonaceous powder is pressurized and molded at a temperature higher than 500°C, so that the adhesion between the particles of the carbonaceous powder progresses in a solid-phase sintering manner.
  • conventional agglomeration using a liquid-phase sintering-like phenomenon excessive particle refinement of caking coal was considered inappropriate because it would lead to a decrease in melting properties.
  • small-particle carbon powder was suitable for agglomeration using a solid-phase sintering-like phenomenon.
  • the method for producing carbon agglomerates comprising the steps of:
  • the carbon agglomerate manufacturing method of the present invention makes it possible to manufacture high-strength carbon agglomerates that can withstand use in a blast furnace, even when the amount of raw carbonaceous material with poor softening and melting properties used is increased.
  • 4 is a graph showing the relationship between the volatile content of carbonaceous powder and the indirect tensile strength of carbon agglomerates in the examples. 4 is a graph showing the relationship between the O/C of carbonaceous powder and the indirect tensile strength of carbon agglomerates in the examples.
  • the method for producing carbon agglomerates includes a powder preparation step of preparing a carbonaceous powder having a volatile content of 6 wt% D.B. or more and less than 20 wt% D.B., an O/C ratio representing the atomic ratio of O atoms to C atoms of 0.040 or more, and a maximum particle size of 300 ⁇ m or less, and a hot press step of pressurizing the carbonaceous powder under conditions of a maximum temperature of 600°C or more and 1250°C or less in an oxygen-blocked environment to obtain a carbon agglomerate.
  • the particles of the carbonaceous powder are bonded to each other by a solid-phase sintering-like phenomenon, rather than a liquid-phase sintering-like phenomenon in which liquid-phase components that can become volatiles are used to bond or fuse the particles of the carbonaceous powder to each other, to form a carbon agglomerate.
  • the powder preparation step includes a step of subjecting raw carbonaceous material to a heat treatment to obtain a heat-treated carbonaceous material, and a step of pulverizing the heat-treated carbonaceous material to obtain the carbonaceous material powder.
  • the raw carbonaceous material to be subjected to the heat treatment, and the carbonaceous powder obtained by heat treating the raw carbonaceous material and optionally pulverizing it may be, for example, one or more types selected from coal and biomass.
  • Biomass is a general term for a certain amount of accumulated plant and animal resources and waste materials originating from these (excluding fossil resources).
  • biomass includes all biomass that produces carbonized material when pyrolyzed, such as agricultural, forestry, livestock, fisheries, and waste materials.
  • the biomass used as the raw carbon material preferably includes biomass with a high effective calorific value, for example wood-based biomass.
  • Wood biomass includes paper by-products such as black pulp liquor and chip dust, lumber by-products such as bark and sawdust, forest residues such as branches, leaves, treetops and end pieces, thinned wood 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 such as willow, poplar, eucalyptus and pine. Wood biomass also includes general waste such as pruned branches from roadside trees in municipalities and private gardens, pruned branches from roadside trees in national and prefectural governments and corporate gardens, and industrial waste such as construction and building waste.
  • wood biomass also includes general waste such as pruned branches from roadside trees in municipalities and private gardens, pruned branches from roadside trees in national and prefectural governments and corporate gardens, and industrial waste such as construction and building waste.
  • Some agricultural biomass such as rice husks, wheat straw, rice straw, sugarcane residue, palm kernel shells, 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 the carbonaceous powder used in the pressure molding is 6 wt% D.B. or more and less than 20 wt% D.B.
  • the volatile content of the carbonaceous powder is less than 6 wt% D.B., it is not possible to obtain carbon agglomerates with sufficient strength to withstand use in a blast furnace.
  • the solid-phase sintering phenomenon in the carbon agglomerate manufacturing method according to this embodiment is thought to be driven by the reaction of the carbonaceous powder becoming aromatic or polycyclic. This reaction involves the elimination of hydrogen and other functional groups, and is accompanied by gas generation.
  • the volatile content of the carbonaceous powder corresponds to the amount of hydrogen and other functional groups that are eliminated when the aromatization or polycyclic reaction that is the driving force of the solid-phase sintering phenomenon occurs, and indicates the potential of the solid-phase sintering phenomenon.
  • the volatile content of the carbonaceous powder is set to 6 wt% D.B. or more, and preferably 8 wt% D.B. or more.
  • the gas generated during heating gas generated by volatilization of volatile content or gas generated by decomposition of volatile content expands, and the carbonaceous powder foams. This inhibits compression of the carbonaceous powder during pressure molding, making it impossible to apply sufficient pressure to the carbonaceous powder, and inhibits the formation of bonds between the particles of the carbonaceous powder due to a solid-phase sintering phenomenon.
  • the gas generated during heating may cause the internal pressure of the space surrounded by the wall of, for example, a mortar or a mold, to exceed the pressure to be applied to the carbonaceous powder during pressure molding.
  • the volatile content of the carbonaceous powder is set to less than 20 wt% D.B., and preferably to 18 wt% D.B. or less.
  • the volatile content of the carbonaceous powder is in the range of 6 wt% D.B. or more and less than 20 wt% D.B., the higher the volatile content, the stronger the carbon agglomerates that can be obtained.
  • the volatile content of the carbonaceous powder is a value measured in accordance with "Coals and cokes - Industrial analysis methods" (JIS M 8812:2004) specified in the Japanese Industrial Standards (JIS).
  • the carbonaceous powder in this embodiment can be obtained through a process of subjecting the raw carbonaceous material to heat treatment to obtain a heat-treated carbonaceous material with a volatile content of 6 wt% D.B. or more and less than 20 wt% D.B., and a process of pulverizing the heat-treated carbonaceous material.
  • the order of pulverization and heat treatment is not limited to this, and the raw carbonaceous material may be pulverized and then heat-treated to obtain carbonaceous powder.
  • the raw carbonaceous material is originally a powder, it is possible to heat-treat the raw carbonaceous material without pulverization to obtain carbonaceous powder with a volatile content of 6 wt% D.B.
  • the raw carbonaceous material may be roughly pulverized and then heat-treated to obtain a volatile content of 6 wt% D.B. or more and less than 20 wt% D.B., and then further pulverized to obtain carbonaceous powder.
  • the heat treatment of the raw carbonaceous material is preferably performed by heating the raw carbonaceous material to a heat treatment temperature of 500°C or more and less than 900°C in an oxygen-blocked environment. If the heat treatment temperature is below 500°C, the volatile matter remaining in the carbonaceous powder will be 20 wt% D.B. or more. Therefore, the heat treatment temperature is preferably 500°C or more, and more preferably 600°C or more. On the other hand, if the heat treatment temperature is 900°C or more, the volatile matter remaining in the carbonaceous powder will be less than 6 wt% D.B., making it difficult for a solid-phase sintering phenomenon to occur.
  • the heat treatment temperature is preferably less than 900°C, and more preferably 800°C or less. Note that, within the range of 500°C or more and less than 900°C, the lower the heat treatment temperature, the more volatile matter in the carbonaceous powder will be, so that a solid-phase sintering phenomenon will be more strongly manifested in the hot pressing process, and a high-strength carbon agglomerate can be obtained.
  • the heat treatment of the raw carbon material is preferably carried out in an atmosphere in which the supply of oxygen is blocked.
  • the heat treatment of the raw carbon material may be carried out while the raw carbon material is contained in a container that prevents the inflow of air and forms a space through which an inert gas flows.
  • the heat treatment of the raw carbon material can be carried out by heating the container that contains the raw carbon material 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 carbonaceous material and the container, and the raw carbonaceous material as a whole can be heat-treated uniformly. In addition, it is possible to perform heat treatment by reliably raising the temperature of the entire raw carbonaceous material to the heat treatment temperature (i.e., by heating evenly), and the quality variation of the heat-treated carbonaceous material and the carbonaceous material powder can be suppressed. There is no particular upper limit for the heat treatment time, but if the heat treatment time is too long, the energy required for the heat treatment increases, which is undesirable as it increases costs. A heat treatment time of 60 minutes or less is usually sufficient.
  • the heat treatment time refers to the time that the temperature of the raw carbon material is maintained at a specified heat treatment temperature of 500°C or higher but less than 900°C from the time it reaches this temperature.
  • Heat treatment can be carried out using heating equipment such as an electric furnace, rotary kiln, fluidized bed heating furnace, screw heating furnace, shaft furnace, or carbonization furnace.
  • heating equipment such as an electric furnace, rotary kiln, fluidized bed heating furnace, screw heating furnace, shaft furnace, or carbonization furnace.
  • the maximum particle size of the carbonaceous powder used in the pressure molding is 300 ⁇ m or less. If the carbonaceous powder contains many coarse particles with particle sizes exceeding 300 ⁇ m, these coarse particles may remain in the carbon agglomerate and reduce its strength. In the subsequent hot pressing process, the solid-phase sintering phenomenon that causes the carbonaceous powder particles to bond together is promoted as the particle size of the carbonaceous powder becomes smaller. Therefore, the remaining coarse particles inhibit the bonding between the particles, causing a decrease in strength. In addition, defects are likely to form around the coarse particles in the carbon agglomerate, which can cause stress concentration and become the starting point of fracture when an external force is applied, resulting in a decrease in strength.
  • the maximum particle size of the carbonaceous powder is preferably 100 ⁇ m or less.
  • the particle size of the carbonaceous powder is appropriately small, the physical structure in the carbon agglomerates becomes dense and homogeneous, which contributes to increasing the strength of the carbon agglomerates.
  • setting the maximum particle size of the carbonaceous powder to less than 20 ⁇ m increases the cost of fine pulverization, but the improvement in the performance of the carbon agglomerates is limited. For this reason, if the maximum particle size of the carbonaceous powder is 20 ⁇ m or more, carbon agglomerates with sufficient strength can be manufactured.
  • the particle size and particle size distribution (volume basis) of the carbonaceous powder can be measured using a commercially available particle size distribution measuring device.
  • a laser diffraction/scattering particle size distribution measuring device "Laser Micronsizer LMS-3000" manufactured by Malvern Panalytical can be used.
  • the particle size distribution of the carbonaceous powder the particle size (circle equivalent particle size) that is 95% of the particles in the carbonaceous powder when calculated from the smallest particles is defined as the maximum particle size.
  • the pulverizing method and pulverizing device for pulverizing the raw carbonaceous material or the heat-treated carbonaceous material are not particularly limited.
  • a media mill such as a cutter mill, a hammer mill, a pin mill, a jet mill, or a ball mill may be used.
  • the pulverizing device is not limited to a device that only performs pulverization, and for example, a pulverizer with a built-in classifier may be used.
  • the O/C ratio which represents the atomic ratio of O atoms to C atoms in the carbonaceous powder used for pressure molding, is 0.040 or more. This can be said in other words that the carbonaceous powder that is the raw material for the carbon agglomerates has many oxygen-containing functional groups.
  • the fact that the carbonaceous powder used for pressure molding has many oxygen-containing functional groups is an important factor in the development of strength.
  • the solid-phase sintering-like phenomenon in the carbon agglomerate manufacturing method of this embodiment is thought to be driven by the aromatization or polycyclization reaction of the carbonaceous powder. Therefore, in order to form bonds between the particles of the carbonaceous powder, the reaction needs to proceed across the particles.
  • a large O/C ratio means that the carbonaceous powder has many oxygen-containing functional groups that can be released when heated. Since the release of oxygen-containing functional groups contributes to the polycyclization reaction of aromatic rings, it is thought that the more oxygen-containing functional groups there are in the carbonaceous powder, the more the polycyclization reaction is promoted and the more likely it is that the solid-phase sintering-like phenomenon will occur.
  • the aromatization or polycyclization reaction of carbonaceous powder proceeds at the edges of crystallites that are composed of relatively planar aromatic ring precursors or layers of monocyclic or polycyclic aromatic carbon. For this reason, in order to form bonds between particles, it is necessary to increase the number of crystallite edges between adjacent particles that are close to each other and have the same stacking direction.
  • carbonaceous powder particles form a packed bed before agglomeration, but since the orientation of each particle cannot be controlled arbitrarily, they are arranged randomly. In addition, it is thought that a solid-phase sintering-like phenomenon occurs only at limited contact surfaces between particles in the packed bed.
  • the O/C of the carbonaceous powder When the O/C of the carbonaceous powder is 0.040 or more, there are sufficient oxygen-containing functional groups necessary for promoting the reaction, and a high-strength carbon agglomerate can be obtained through a solid-phase sintering phenomenon.
  • the O/C of the carbonaceous powder When the O/C of the carbonaceous powder is less than 0.040, the solid-phase sintering phenomenon does not proceed sufficiently, making it difficult to obtain a high-strength carbon agglomerate. Therefore, it is important that the O/C of the carbonaceous powder is 0.040 or more, and it is more preferable that it is 0.045 or more. The higher the O/C of the carbonaceous powder, the better, so there is no particular upper limit, but the O/C of the carbonaceous powder can be 0.12 or less.
  • Charcoal powder with an O/C of 0.040 or more can be obtained by, for example, crushing heat-treated raw carbonaceous material obtained by heat-treating raw carbonaceous material that has not been significantly subjected to the coalification action, such as low-coalification coal or biomass.
  • the caking coal used in normal coke production has a reduced O/C due to decarbonation gasification by pressurization and heating during the coalification process, so the heat-treated carbonaceous material obtained by heat-treating it and the carbonaceous powder obtained by further crushing it both have a low O/C and are unlikely to undergo solid-phase sintering-like phenomena.
  • the heat-treated carbonaceous material obtained by heat-treating such raw carbonaceous material and the carbonaceous powder obtained by further crushing it both have a high O/C and are likely to favorably undergo solid-phase sintering-like phenomena.
  • the atomic ratio O/C of O atoms to C atoms in the carbonaceous powder is calculated from the results of quantifying O and C according to the "Elemental analysis method for coals and cokes" (JIS M 8813:2004) specified in JIS.
  • the carbonaceous powder obtained in the powder preparation step is pressurized and molded under conditions in which the maximum temperature is 600° C. or more and 1250° C. or less in an oxygen-blocking environment to obtain a carbon agglomerate.
  • the carbonaceous powder is mechanically pressed and molded, i.e., pressurized.
  • Mechanical pressing means compressing the carbonaceous powder with a physical wall member such as a pestle and mortar, a mold, or a compression roll.
  • the carbonaceous powder is pressurized (i.e., hot pressed) while it is being heated.
  • Pressing the carbonaceous powder while it is being heated includes cases where pressurization is applied only during a part of the entire process of heating the carbonaceous powder, and cases where pressurization is applied throughout the entire process.
  • Heating the carbonaceous powder refers to the state in which the temperature of the carbonaceous powder is being increased.
  • the hot press device for pressurizing and molding the carbonaceous powder while heating it is not particularly limited.
  • the carbonaceous powder can be pressurized by storing the carbonaceous powder in a space surrounded by the above-mentioned walls (for example, in a mold for hot pressing) and compressing it through the walls.
  • the heat source for heating the carbonaceous powder can be, for example, electrical resistance heating, microwave heating, or high-frequency induction heating.
  • the carbonaceous powder may be heated through the wall during the hot pressing process.
  • the temperature of the carbonaceous powder at the start of pressing the carbonaceous powder during the hot pressing process is referred to as the “molding start temperature,” and the maximum temperature of the carbonaceous powder during the pressing period is referred to as the “maximum reached temperature.”
  • the maximum temperature reached during the hot pressing process must be between 600°C and 1250°C. This is because in this temperature range, the bonding between particles occurs significantly due to a solid-phase sintering-like phenomenon.
  • the maximum temperature reached in the hot pressing process is less than 600°C, the bonding between particles due to a solid-phase sintering phenomenon will not proceed sufficiently. From the viewpoint of ensuring that the bonding between particles due to a solid-phase sintering phenomenon proceeds sufficiently, the maximum temperature reached should be 600°C or higher, preferably 700°C or higher, and more preferably 900°C or higher.
  • the maximum temperature reached in the hot pressing process exceeds 1250°C, the detachment of hetero elements occurs, the bonding between particles does not progress sufficiently, and the formation of bonds between particles due to a solid-phase sintering phenomenon is inhibited. Therefore, the maximum temperature reached should be 1250°C or less, and preferably 1100°C or less.
  • a carbonization process may be further carried out after the hot pressing process. That is, after pressure molding, the load may be removed, and the carbon agglomerates may be continuously heated in an unpressurized state for carbonization.
  • the carbonization temperature (the maximum temperature of the carbon agglomerates during the carbonization process) is higher than the maximum temperature reached in the hot pressing process.
  • the carbonization temperature is set to 1250°C or less, and preferably 1100°C or less. Note that in this embodiment, the heating in the hot pressing process can also serve as the carbonization process, so the carbonization process after hot pressing is optional.
  • the rate of temperature rise from the molding start temperature to the maximum temperature is preferably 1°C/min or more and 30°C/min or less. By setting the rate of temperature rise to 1°C/min or more and 30°C/min or less, it is possible to avoid a decrease in strength.
  • the holding time at the maximum temperature is preferably 1 minute or more from the viewpoint of suppressing strength variations due to temperature unevenness in the carbon agglomerate. Furthermore, holding at the maximum temperature for a long period of time does not result in any significant improvement in performance, while there is a problem of reduced productivity, so the holding time is preferably 60 minutes or less.
  • the pressure mechanically applied to the carbonaceous powder in the hot pressing process is called the molding pressure.
  • the higher the molding pressure the more contact points there are between the particles of the carbonaceous powder, promoting a solid-phase sintering phenomenon. Therefore, the higher the molding pressure, the stronger the carbon agglomerates will be.
  • the molding pressure is 11 MPa or more, the strength of the carbon agglomerates will be stable. If the molding pressure is less than 11 MPa, it may not be possible to obtain high-strength carbon agglomerates. Therefore, the molding pressure is preferably 11 MPa or more, and more preferably 20 MPa or more. However, if the molding pressure is too high, the manufacturing costs may increase. A molding pressure of 300 MPa or less is sufficient.
  • Carbon agglomerates According to the method for producing carbon agglomerates of this embodiment, it is possible to produce carbon agglomerates having high strength capable of withstanding use in a blast furnace without using any liquid phase components.
  • a carbon agglomerate having a strength of 4 MPa or more is evaluated as having a strength capable of being used in a conventional blast furnace process (i.e., high-strength coke).
  • the strength of the carbon agglomerates refers to their cold indirect tensile strength measured by the method described in Non-Patent Document 1.
  • carbon agglomerate refers to an agglomerate that is mainly made of carbon and is manufactured by the manufacturing method according to this embodiment, and has a carbon content of 70 wt% D.B. or more and 100 wt% D.B. or less.
  • the raw carbonaceous material shown in Table 1 was subjected to heat treatment to obtain heat-treated carbonaceous material.
  • the heat treatment was carried out in an electric furnace with nitrogen gas circulating, under conditions where the raw carbonaceous material was heated to the heat treatment temperature shown in Table 1 and then held for 30 minutes.
  • the heat-treated carbonaceous material was then pulverized to obtain carbonaceous powder having the maximum particle size shown in Table 1.
  • An ultracentrifugal pulverizer (Verder Scientific, model: ZM200) was used for the pulverization process.
  • Table 1 also shows the volatile content and O/C of the carbonaceous powder.
  • the carbonaceous powder was heated at a heating rate of 20°C/min until it reached the molding start temperature shown in Table 1 under nitrogen gas flow without applying molding pressure, and then the carbonaceous powder was heated at a heating rate of 20°C/min until it reached the maximum temperature shown in Table 1 while applying the molding pressure shown in Table 1. The carbonaceous powder was then held at the maximum temperature shown in Table 1 for 5 minutes. The carbon agglomerates obtained were then cooled and collected.
  • the indirect tensile strength of the obtained carbon agglomerates was measured.
  • the indirect tensile strength was measured according to the method described in Non-Patent Document 1.
  • Table 1 shows the indirect tensile strength of the carbon agglomerates in each example.
  • Figure 1 is a graph showing the relationship between the volatile content of the carbon powder and the indirect tensile strength of the carbon agglomerates in the examples (invention examples No. 1 to 9 and comparison examples No. 10 to 18).
  • Figure 2 is a graph showing the relationship between the O/C of the carbon powder and the indirect tensile strength of the carbon agglomerates in the examples (invention examples No. 1 to 9 and comparison examples No. 10 to 18).
  • Table 1 shows the indirect tensile strength of the carbon agglomerates in each example.
  • Figure 1 is a graph showing the relationship between the volatile content of the carbon powder and the indirect tensile strength of the carbon agglomerates in the examples (invention examples No. 1 to 9 and comparison examples
  • the method for producing carbon agglomerates of the present invention it is possible to produce carbon agglomerates having high strength capable of withstanding use in a blast furnace, even when the amount of raw carbonaceous material having poor thermoplasticity is increased.

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PCT/JP2023/045365 2023-04-28 2023-12-18 炭素塊成化物の製造方法 Ceased WO2024224682A1 (ja)

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EP23935453.3A EP4656617A1 (en) 2023-04-28 2023-12-18 Method for producing carbon briquette

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS542A (en) * 1977-06-03 1979-01-05 Maruzen Sekiyu Kagaku Kk Production of raw coke compositions for produing carbonaceous materials
JPS58185416A (ja) * 1982-04-21 1983-10-29 Hitachi Chem Co Ltd 炭素質慴動材の製造法
JPS58165756U (ja) * 1982-04-28 1983-11-04 アルプス電気株式会社 記録媒体の走行ガイド部材
JPS6172610A (ja) * 1984-09-14 1986-04-14 Hitachi Chem Co Ltd 高密度黒鉛材の製造法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61122110A (ja) 1984-11-16 1986-06-10 Agency Of Ind Science & Technol 高密度炭素材の製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS542A (en) * 1977-06-03 1979-01-05 Maruzen Sekiyu Kagaku Kk Production of raw coke compositions for produing carbonaceous materials
JPS58185416A (ja) * 1982-04-21 1983-10-29 Hitachi Chem Co Ltd 炭素質慴動材の製造法
JPS58165756U (ja) * 1982-04-28 1983-11-04 アルプス電気株式会社 記録媒体の走行ガイド部材
JPS6172610A (ja) * 1984-09-14 1986-04-14 Hitachi Chem Co Ltd 高密度黒鉛材の製造法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP4656617A1 *

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