WO2022201828A1 - Système d'alimentation en gaz de cémentation et système de cémentation - Google Patents

Système d'alimentation en gaz de cémentation et système de cémentation Download PDF

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Publication number
WO2022201828A1
WO2022201828A1 PCT/JP2022/002544 JP2022002544W WO2022201828A1 WO 2022201828 A1 WO2022201828 A1 WO 2022201828A1 JP 2022002544 W JP2022002544 W JP 2022002544W WO 2022201828 A1 WO2022201828 A1 WO 2022201828A1
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Prior art keywords
carburizing
gas
carbon dioxide
unit
supply system
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PCT/JP2022/002544
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English (en)
Japanese (ja)
Inventor
章 軍司
晃平 吉川
昌俊 杉政
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Hitachi Ltd
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Hitachi Ltd
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D17/00—Arrangements for using waste heat; Arrangements for using, or disposing of, waste gases
    • F27D17/20—Arrangements for treatment or cleaning of waste gases
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/06—Surface hardening
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/74—Methods of treatment in inert gas, controlled atmosphere, vacuum or pulverulent material
    • C21D1/76—Adjusting the composition of the atmosphere
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/23—Carbon monoxide or syngas
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C25B15/02—Process control or regulation
    • C25B15/023—Measuring, analysing or testing during electrolytic production
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/01—Products
    • C25B3/03—Acyclic or carbocyclic hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D19/00—Arrangements of controlling devices
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D21/00—Arrangement of monitoring devices; Arrangement of safety devices
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D7/00—Forming, maintaining or circulating atmospheres in heating chambers
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D7/00—Forming, maintaining or circulating atmospheres in heating chambers
    • F27D7/02—Supplying steam, vapour, gases or liquids

Definitions

  • the present invention relates to a carburizing gas supply system that supplies a carburizing gas to a carburizing furnace that performs carburizing, and a carburizing system that uses the carburizing gas supply system.
  • a gas called RX gas containing hydrogen (H 2 ), carbon monoxide (CO), and nitrogen (N 2 ) as main components is produced by reacting a hydrocarbon such as methane (CH 4 ) with air. is generated and supplied to the carburizing furnace as a base gas.
  • the carburizing process is controlled by adjusting the carbon potential (CP) in the carburizing furnace by adding hydrocarbons called enriched gas to the RX gas as needed.
  • the carbon potential can be estimated from the composition and temperature of the carburizing gas, which is the RX gas or the RX gas to which the enriched gas is added, and can be controlled by the supply flow rate of the enriched gas.
  • carburizing gas with controlled carbon potential is continuously supplied to the carburizing furnace in order to maintain the atmosphere in the carburizing furnace.
  • most of the carbon monoxide and hydrogen contained in the carburizing gas are discharged to the outside of the carburizing furnace without reacting, and are exhausted after being burned. Therefore, there is a problem of consuming a lot of fuel.
  • effective utilization of the exhaust gas discharged from the carburizing furnace has been proposed.
  • Patent Document 1 exhaust gas discharged from a carburizing furnace is recovered, water vapor (H 2 O) and carbon dioxide (CO 2 ) are removed from the exhaust gas, and the exhaust gas after removing water vapor and carbon dioxide is disclosed.
  • a gas supply system that recycles is described.
  • the present invention has been made in view of the above problems, and can reduce carbon dioxide emissions, reduce the amount of new carburizing gas used, and supply an optimum gas composition according to the conditions inside the furnace.
  • a main object of the present invention is to provide a carburizing gas supply system and a carburizing system.
  • the carburizing gas supply system of the present invention provides a carburizing gas supply system that supplies a carburizing gas to a carburizing furnace that performs carburizing treatment, comprising: , a first flow rate measurement unit for measuring the flow rate of the exhaust gas, a first concentration measurement unit for measuring the concentration of the components of the exhaust gas, a first supply unit for supplying carbon dioxide to the exhaust gas, and the flow rate of the exhaust gas.
  • control unit that controls the supply amount of the carbon dioxide based on the concentrations of the above components, a carbon dioxide conversion unit that generates hydrocarbons or carbon monoxide from carbon dioxide and removes water or oxygen, and the carbon dioxide a carburizing gas supply unit for supplying the regenerated carburizing gas containing the hydrocarbons or carbon monoxide generated in the converting unit to the carburizing furnace.
  • a carburizing system includes the carburizing gas supply system and a carburizing furnace for carburizing.
  • This specification includes the disclosure content of Japanese Patent Application No. 2021-051216, which is the basis of priority of this application.
  • the amount of carbon dioxide emissions can be reduced, the amount of new carburizing gas used can be reduced, and the optimum gas composition can be supplied according to the conditions inside the furnace.
  • FIG. 1 is a diagram showing an outline of a carburizing gas supply system and a carburizing system according to Embodiment 1.
  • FIG. 1 shows an outline of a carburizing gas supply system and a carburizing system according to a modification of the first embodiment, in which the carburizing gas supply system measures the flow rate of the gas supplied to the carburizing furnace and the concentration of the components of the gas;
  • FIG. 4 is a diagram showing;
  • FIG. 5 is a diagram showing an outline of a carburizing gas supply system and a carburizing system according to Embodiment 2;
  • FIG. 10 is a diagram showing an outline of a carburizing gas supply system and a carburizing system according to Embodiment 3;
  • FIG. 10 is a diagram showing an outline of a carburizing gas supply system and a carburizing system according to Embodiment 4;
  • 1 is a schematic diagram of a conventional carburizing gas supply system and a carburizing system;
  • the material may be selected singly or in combination as long as it is not inconsistent with the content disclosed in this specification. , materials other than those exemplified below may be selected as long as they are consistent with what is disclosed herein.
  • FIG. 1 is a schematic diagram of a carburizing gas supply system and a carburizing system according to Embodiment 1.
  • FIG. 6 is a schematic diagram of a conventional carburizing system.
  • a conventional carburizing system 100 includes an RX gas generator 1, an enriched gas supply unit 2, a carburizing furnace 3, a combustion facility 4, and a gas flow path 20, as shown in FIG.
  • the carburizing system 100 according to the first embodiment includes an RX gas generator 1, an enriched gas supply unit 2, a carburizing furnace 3, a carburizing gas supply system 50, a combustion facility 4, a gas flow path 20.
  • the RX gas generator 1 reacts a hydrocarbon such as methane (CH 4 ) with air to produce RX gas, which is mainly composed of hydrogen (H 2 ), carbon monoxide (CO), and nitrogen (N 2 ). and is supplied to the carburizing furnace 3 through the gas flow path 20 and the supply port 3a.
  • the enriched gas supply unit 2 adds a hydrocarbon called enriched gas to the RX gas as necessary, and supplies the RX gas to the carburizing furnace 3 via the supply port 3a via the gas flow path 20 .
  • the composition of the RX gas is not particularly limited, for example, it contains 40% by volume of hydrogen, 20% by volume of carbon monoxide, and 40% by volume of nitrogen, in addition to some carbon dioxide (CO 2 ) and water vapor (H 2 O).
  • the enriched gas include, but are not limited to, methane (CH 4 ), propane (C 3 H 8 ), and the like.
  • RX gas or a gas obtained by adding enriched gas to RX gas is supplied as a new carburizing gas.
  • the carburizing furnace 3 uses a new carburizing gas to carburize the steel material placed in the carburizing furnace 3 . Specifically, in the carburizing treatment, carbon is diffused from the surface of the steel material. After the new carburizing gas has been used for the carburizing process, the gas is discharged as exhaust gas from the carburizing furnace 3 to the gas flow path 20 through the discharge port 3b.
  • Exhaust gas contains carbon dioxide and water vapor (water) in addition to hydrogen, carbon monoxide, and nitrogen.
  • composition of the exhaust gas is not particularly limited, it contains, for example, a total of 55 to 59% by volume of hydrogen and carbon monoxide, a total of 1 to 4% by volume of carbon dioxide and water vapor, and 40 to 43% by volume of nitrogen.
  • a carburizing gas supply system 50 is a carburizing gas supply system that supplies a carburizing gas to a carburizing furnace 3, and includes a gas discharge section 30, a first flow rate measuring section 5, and a first concentration measuring section. 6, a first supply unit 8, a second supply unit 9, a third supply unit 15, a control unit 7, a carbon dioxide conversion unit 10, a pressure increasing unit 13, a reforming reaction unit 14, and for carburizing A gas supply unit 40 and a gas flow path 20 are provided.
  • the gas discharge part 30 is composed of an outlet 3b of the carburizing furnace 3 and a gas flow path 20 connected to the outlet 3b, and discharges exhaust gas from the carburizing furnace 3 to the gas flow path 20 through the outlet 3b.
  • the gas flow path 20 is branched downstream of the gas discharge section 30 and connected to the combustion equipment 4 and the first flow rate measurement section 5 respectively.
  • exhaust gas discharged from the carburizing furnace 3 is introduced into the first flow rate measuring section 5 through the gas flow path 20 . All of the exhaust gas discharged from the carburizing furnace 3 can be introduced into the first flow rate measuring unit 5, or only a part of it can be introduced into the first flow rate measuring unit 5.
  • the first flow rate measuring section 5 it is preferable to introduce all of them into the first flow rate measuring section 5 .
  • the rest of the exhaust gas that is not introduced into the first flow rate measuring unit 5 is introduced into the combustion facility 4 via the gas flow path 20, and discharged outside after detoxification.
  • the first flow rate measurement unit 5 measures the flow rate of the exhaust gas introduced into the first flow rate measurement unit 5 . After the flow rate measurement, the exhaust gas is introduced into the first concentration measuring section 6 via the gas flow path 20 .
  • the first concentration measuring section 6 measures the concentrations of the components of the exhaust gas introduced into the first concentration measuring section 6 .
  • the first concentration measuring unit 6 is not particularly limited as long as it measures the concentration of the exhaust gas component that enables the estimation of the carbon consumption, which will be described later.
  • the first concentration measuring unit 6 may measure the concentration of some or all of the components of the exhaust gas. For example, it may be one that measures the concentration of at least carbon dioxide among the components of the exhaust gas.
  • FIG. 2 shows a carburizing gas supply system and a carburizing system according to a modified example of the first embodiment, in which the flow rate of the gas supplied to the carburizing furnace by the carburizing gas supply system and the concentration of the components of the gas are measured. It is a figure which shows the outline of what was made to carry out.
  • the carburizing gas supply system 50 further includes a second flow rate measuring section 21 and a second concentration measuring section 22 in addition to the configuration of the carburizing gas supply system 50 shown in FIG. .
  • the second flow rate measuring unit 21 measures the flow rate of the regeneration carburizing gas supplied to the carburizing furnace 3 .
  • the second concentration measuring unit 22 measures the concentration of the components of the regeneration carburizing gas supplied to the carburizing furnace 3 .
  • the second flow rate measurement unit 21 and the second 2 By measuring the flow rate of the regenerating carburizing gas and the concentration of the components of the regenerating carburizing gas by the concentration measuring unit 22, it becomes easier to estimate the amount of carbon consumed in the carburizing furnace, and the gas to be supplied to the carburizing furnace can be easily estimated. It becomes even easier to supply the optimum gas composition.
  • the first supply unit 8 supplies carbon dioxide to the exhaust gas on the downstream side of the first concentration measurement unit 6 in the gas flow path 20 .
  • the second supply unit 9 supplies hydrogen to the exhaust gas on the downstream side of the first concentration measurement unit 6 in the gas flow path 20 .
  • the control unit 7 determines the supply amount of carbon dioxide supplied to the exhaust gas by the first supply unit 8 based on the flow rate and component concentrations of the exhaust gas measured by the first flow rate measurement unit 5 and the first concentration measurement unit 6, and the amount of hydrogen supplied to the exhaust gas by the second supply unit 9 is controlled.
  • a method for controlling the amount of carbon dioxide supplied and the amount of hydrogen supplied will be described in detail.
  • the amount of carbon added to the steel material from the new carburizing gas and consumed from the new carburizing gas is determined by the flow rate and the composition of the exhaust gas. can be estimated from the concentration of Specifically, as a method for estimating the amount of carbon consumed, for example, carbon is added to the steel material by the reaction shown in formula (1) in the carburizing process, so the amount of carbon consumed is the same amount of substance as the increase in carbon dioxide Based on the premise that it will be After obtaining the amount of increase, the amount of carbon consumption is estimated from the amount of increase in the flow rate of the exhaust gas and the carbon dioxide concentration. Note that even when carbon dioxide reacts according to equation (5) described later, the amount of carbon consumed can be estimated by measuring the water vapor concentration.
  • the flow rate of carbon dioxide supplied to the exhaust gas by the first supply unit 8 is adjusted so that the same amount of carbon as the amount of carbon consumed is supplied to the exhaust gas. Control. Furthermore, based on the flow rate and component concentration of the exhaust gas, the flow rate of carbon dioxide contained in the exhaust gas is calculated, and the flow rate of carbon dioxide contained in the exhaust gas and the amount of carbon dioxide supplied to the exhaust gas by the first supply unit 8 The flow rate of hydrogen supplied to the exhaust gas by the second supply unit 9 is controlled so that the flow rate of the substance amount is the same as the total flow rate. As described above, the supply amount of carbon dioxide and the supply amount of hydrogen are controlled. As a result, the carbon dioxide conversion section 10 and the reforming reaction section 14 can generate reformed gas having the same composition as the carburizing gas.
  • the hydrogen supply source of the second supply unit 9 is not particularly limited, for example, from the viewpoint of suppressing the use of fossil fuels, hydrogen generated from a water electrolysis device (electrolysis device) is preferable.
  • the second supply unit 9 may supply water vapor together with hydrogen to the exhaust gas. Thereby, carbon deposition in the methanation reaction section 11 can be suppressed.
  • the control unit 7 can also control the supply amount of water vapor supplied to the exhaust gas by the second supply unit 9 based on the flow rate and component concentration of the exhaust gas.
  • the third supply section 15 may supply water vapor to the exhaust gas on the downstream side of the first concentration measurement section 6 in the gas flow path 20 . Thereby, carbon deposition in the methanation reaction section 11 can be suppressed.
  • the control unit 7 can also control the amount of water vapor supplied to the exhaust gas by the third supply unit 15 based on the flow rate and component concentration of the exhaust gas.
  • the carbon dioxide conversion section 10 is arranged downstream of the first concentration measurement section 6 in the gas flow path 20, generates hydrocarbons or carbon monoxide from carbon dioxide, and removes water or oxygen.
  • the carbon dioxide conversion unit 10 according to Embodiment 1 has a methanation reaction unit 11 and a water vapor removal unit 12 .
  • the methanation reaction unit 11 generates methane (hydrocarbon) and water vapor (water) by catalytic reaction from the exhaust gas and the mixed gas of carbon dioxide and hydrogen supplied to the exhaust gas.
  • methane and water vapor are generated from carbon dioxide and hydrogen contained in the mixed gas by advancing the methanation reaction represented by the formula (2) through a catalytic reaction.
  • the methanation reaction represented by Formula (3) proceeds simultaneously with the reaction represented by Formula (2).
  • the reaction represented by formula (3) methane and water vapor are produced from carbon monoxide and hydrogen contained in the mixed gas.
  • the reaction temperature of the reaction represented by the formula (2) in the methanation reaction section 11 is preferably 500° C. to 600° C. from the viewpoint of suppressing the progress of the reaction represented by the formula (3).
  • the mixed gas is converted into the converted gas by the reactions shown in the formulas (2) and (3).
  • an appropriate reactor is selected to allow the reaction shown in formula (2) to proceed.
  • the catalyst used in the methanation reaction section 11 is not particularly limited, but examples thereof include Ni-based catalysts.
  • the water vapor removal unit 12 removes water vapor from the converted gas and discharges it to the outside.
  • a method for removing water vapor is not particularly limited, but examples thereof include condensation by cooling, adsorption separation, membrane separation, and the like.
  • the amount of water vapor to be removed is the same amount of oxygen as the oxygen contained in the carbon dioxide supplied to the exhaust gas by the first supply unit 8, and the same amount of hydrogen as the amount of hydrogen supplied to the exhaust gas by the second supply unit 9. of hydrogen is adjusted to be removed from the converted gas. Further, when water vapor is supplied to the exhaust gas by at least one of the third supply unit 15 and the second supply unit 9, the amount of water vapor removed by at least one of the third supply unit 15 and the second supply unit 9 is The same material amount of water vapor as was supplied to is also arranged to be removed from the converted gas. As described above, the reforming reaction section 14 can generate a reformed gas having the same composition as the carburizing gas.
  • the pressurizing section 13 is arranged downstream of the carbon dioxide conversion section 10 in the gas flow path 20, sucks the exhaust gas discharged from the carburizing furnace 3 into the gas flow path 20, and produces a reformed gas in the reforming reaction section 14.
  • the gas is pressurized so as to obtain a pressure for supplying to the carburizing furnace 3.
  • the boosting unit 13 is not particularly limited, but for example, a blower, a pump, or the like can be selected.
  • the converted gas from which water vapor has been removed is introduced into the reforming reaction section 14 via the gas flow path 20 .
  • the reforming reaction section 14 is arranged downstream of the pressurizing section 13 in the gas flow path 20, and produces carbon monoxide and hydrogen by catalytic reaction from methane contained in the converted gas after water vapor removal.
  • carbon monoxide and hydrogen are generated from methane and water vapor contained in the converted gas after water vapor removal by advancing the reaction shown in formula (4) through a catalytic reaction. Furthermore, by advancing the reaction shown in Formula (5) together with the reaction shown in Formula (4), carbon monoxide and water vapor are generated from carbon dioxide and hydrogen contained in the converted gas after water vapor removal.
  • the reaction temperature of the reactions represented by formulas (4) and (5) in the reforming reaction section 14 is 900 from the viewpoint of suppressing carbon deposition and generating a reformed gas having the same composition as the carburizing gas. °C or higher is preferred. Moreover, from the viewpoint of suppressing deterioration of the reforming catalyst, the temperature is preferably 1200° C. or less. Moreover, from the viewpoint of making the composition similar to that of the carburizing gas, the same temperature as that of the RX gas generation section is preferable.
  • the converted gas from which water vapor has been removed is reformed by the reactions shown in formulas (4) and (5) to generate a reformed gas.
  • an appropriate reactor is selected to allow the reactions shown in formulas (4) and (5) to proceed.
  • the reactor used as the RX gas generation section 1 may also be used.
  • the catalyst used in the reforming reaction section 14 is not particularly limited, but examples thereof include Ni-based catalysts.
  • the carburizing gas supply unit 40 is composed of the supply port 3a of the carburizing furnace 3 and the gas flow path 20 connected to the supply port 3a. , through the gas passage 20 and through the supply port 3a to the carburizing furnace 3.
  • the carburizing gas supply system 50 while reusing hydrogen, carbon monoxide, and nitrogen contained in the exhaust gas, carbon monoxide is regenerated from carbon dioxide, water vapor, etc. generated in the carburizing process. is doing. Therefore, the amount of carbon dioxide emissions can be reduced, and carbon monoxide can be regenerated from carbon dioxide, water vapor, and the like with little energy consumption. Furthermore, the amount of RX gas generated by the RX gas generator 1 and the amount of enriched gas added by the enriched gas supply unit 2 can be reduced according to the amount of the reformed gas supplied to the carburizing furnace 3 as the regeneration carburizing gas. . That is, the amount of new carburizing gas used can be reduced. As a result, energy consumption can be reduced during the entire process for carburizing with the carburizing system 100 . Moreover, since the amount of methane consumed by the RX gas generator 1 can be reduced, costs can be reduced.
  • the first supply unit 8 supplies carbon dioxide to the exhaust gas based on the flow rate and component concentrations of the exhaust gas measured by the first flow rate measurement unit 5 and the first concentration measurement unit 6.
  • the supply amount of hydrogen supplied to the exhaust gas by the second supply unit 9 and the supply amount of water vapor supplied to the exhaust gas by the third supply unit 15 or the like can be controlled to optimum amounts.
  • the carbon potential (CP) in the carburizing furnace can be adjusted to an optimum value by adjusting the amount of components such as carbon monoxide and hydrogen contained in the reformed gas to an optimum amount.
  • the carburizing gas supply system 50 preferably operates using renewable energy as electric power.
  • FIG. 3 is a schematic diagram of a carburizing gas supply system and a carburizing system according to a second embodiment.
  • the carburizing gas supply system 50 according to the second embodiment is arranged downstream of the first concentration measuring unit 6 and upstream of the carbon dioxide conversion unit 10 in the gas flow path 20, in addition to the configuration according to the first embodiment.
  • a flow control unit 16 is further provided.
  • the carburizing gas supply system 50 according to the second embodiment does not include the third supply section 15 .
  • the flow control unit 16 branches the exhaust gas after the concentration measurement, thereby introducing a part of the exhaust gas into the methanation reaction unit 11 of the carbon dioxide conversion unit 10 via the gas flow path 20, and transferring the remaining exhaust gas to By flowing it to the downstream side of the carbon dioxide conversion section 10 through the gas flow path 20 , the gas is directly introduced into the reforming reaction section 14 .
  • the first supply unit 8 supplies carbon dioxide to a portion of the exhaust gas introduced into the methanation reaction unit 11, and the second supply unit 9 supplies carbon dioxide to a portion of the exhaust gas introduced into the methanation reaction unit 11. Hydrogen is supplied to part of the exhaust gas introduced into the section 11 . Then, a part of the exhaust gas and a mixed gas in which carbon dioxide and hydrogen supplied to the exhaust gas are mixed are introduced into the methanation reaction section 11 of the carbon dioxide conversion section 10 via the gas flow path 20 .
  • the reaction temperature of the reaction represented by formula (2) in the methanation reaction section 11 is preferably 200°C to 300°C from the viewpoint of increasing the reaction rate.
  • the reforming reaction unit 14 generates a reformed gas in which the remainder of the exhaust gas not introduced into the methanation reaction unit 11 and the converted gas after the removal of water vapor are reformed by the reactions shown in formulas (4) and (5). .
  • the supply amount of carbon dioxide and the amount of hydrogen supplied in the first supply unit 8 and the second supply unit 9 are different from those described above. and the amount of water vapor removed by the water vapor removal unit 12 are the same as those of the first embodiment.
  • the amount of exhaust gas introduced into the methanation reaction unit 11 is reduced by branching the exhaust gas after concentration measurement by the flow control unit 16, thereby reducing the amount of the exhaust gas introduced into the methanation reaction unit 11. size can be reduced.
  • the ratio of the flow rate of the exhaust gas to which carbon dioxide is supplied to the flow rate of carbon dioxide supplied to the exhaust gas is reduced. Therefore, carbon deposition in the methanation reaction section 11 can be suppressed.
  • the amount of methane produced in the methanation reaction section 11 can be controlled by causing the flow control section 16 to partially flow the exhaust gas after the concentration measurement to the bypass channel and to the downstream side of the carbon dioxide conversion section 10. Since it becomes possible, it becomes easy to control the reaction.
  • FIG. 4 is a schematic diagram of a carburizing gas supply system and a carburizing system according to the third embodiment.
  • a separation section 17 (separation section) is further provided.
  • the carbon dioxide conversion unit 10 is arranged downstream of the separation unit 17 in the gas flow path 20, and includes the methanation reaction unit 11 or the carbon monoxide generation reaction unit 18 and the water vapor removal unit 12.
  • the carburizing gas supply system 50 does not include the third supply section 15 .
  • the pressurizing section 13 is arranged downstream of the first concentration measuring section 6 and upstream of the separating section 17 .
  • the separation unit 17 separates water vapor (water) and carbon dioxide from the exhaust gas whose concentration has been measured, and passes the separated gas containing water vapor and carbon dioxide as main components to the carbon dioxide conversion unit 10 through the gas flow path 20.
  • the separation unit 17 By introducing the waste gas into the methanation reaction unit 11 or the carbon monoxide generation reaction unit 18 and flowing the remainder of the exhaust gas after the separation gas is separated downstream of the carbon dioxide conversion unit 10 through the gas flow path 20, It is introduced into the reforming reaction section 14 as it is.
  • the separation method of the separation gas of the separation unit 17 is not particularly limited, but includes, for example, adsorption separation, membrane separation, and the like.
  • the adsorbent used for adsorptive separation is not particularly limited, but examples thereof include zeolite, ceria, molecular sieves, activated carbon and the like.
  • the first supply unit 8 supplies carbon dioxide to the separation gas downstream of the separation unit 17 in the gas flow path 20, and the second supply unit 9 supplies the gas flow Hydrogen is supplied to the separation gas downstream of separation section 17 in line 20 . Then, the separation gas and the mixed gas of carbon dioxide and hydrogen supplied to the separation gas are supplied to the methanation reaction section 11 or the carbon monoxide generation reaction section 18 of the carbon dioxide conversion section 10 through the gas flow path 20. be introduced.
  • methane and water vapor are generated from carbon dioxide and hydrogen contained in the mixed gas by advancing the methanation reaction represented by the formula (2) through a catalytic reaction.
  • the reaction temperature of the reaction represented by formula (2) in the methanation reaction section 11 is preferably 200° C. to 300° C. from the viewpoint of increasing the reaction rate.
  • the mixed gas is converted by the reaction represented by the formula (2) as described above to generate a converted gas.
  • the carbon monoxide generation reaction unit 18 generates carbon monoxide and water vapor from carbon dioxide and hydrogen contained in the mixed gas by advancing the reaction shown in formula (5) through a catalytic reaction.
  • the reaction temperature of the reaction represented by formula (5) in the carbon monoxide generation reaction section 18 is preferably 700°C or higher from the viewpoint of increasing the reaction rate. Moreover, from the viewpoint of suppressing deterioration of the catalyst, the temperature is preferably 1200° C. or less.
  • an appropriate reactor is selected to allow the reaction shown in the formula (5) to proceed.
  • the catalyst used in the carbon monoxide generation reaction unit 18 is not particularly limited, but examples thereof include Ni-based catalysts and Cu-based catalysts. Cu-based catalysts are preferable from the viewpoint of suppressing the generation of methane.
  • the carbon monoxide generation reaction section 18 may also serve as the water vapor removal section 12 by mixing zeolite with a catalyst and selectively adsorbing water vapor. In that case, the reaction represented by formula (5) proceeds even at low temperatures, so the reaction temperature can be reduced to 300° C. or lower.
  • the mixed gas is converted by the reaction represented by the formula (5) as described above to generate a converted gas.
  • the reforming reaction section 14 is arranged on the downstream side of the separation section 17 in the gas flow path 20, and the remainder of the exhaust gas after the separation gas is separated and the converted gas after removal of water vapor are expressed by the formulas (4) and (5). ) to generate a reformed gas reformed by the reaction shown in ).
  • the supply amount of carbon dioxide and the amount of hydrogen supplied in the first supply unit 8 and the second supply unit 9 are different from those described above. and the amount of water vapor removed by the water vapor removal unit 12 are the same as those of the first embodiment.
  • Embodiment 3 water vapor and carbon dioxide are separated from the exhaust gas after concentration measurement by the separation unit 17, and the separated gas containing water vapor and carbon dioxide as main components is converted to the methanation reaction unit 11 or the carbon monoxide generation reaction. Since it is introduced into the methanation reaction unit 11 or the carbon monoxide generation reaction unit 18, the concentration of water vapor, carbon dioxide, etc. in the mixed gas to be reacted in the methanation reaction unit 11 or the carbon monoxide generation reaction unit 18 can be improved. Carbon deposition in the production reaction section 18 can be suppressed. Furthermore, the reaction in the methanation reaction section 11 or the carbon monoxide generation reaction section 18 is facilitated because it is not affected by hydrogen or carbon monoxide.
  • FIG. 5 is a schematic diagram of a carburizing gas supply system and a carburizing system according to a fourth embodiment.
  • the carbon dioxide conversion section 10 has the electrolytic reaction section 19 instead of the methanation reaction section 11 or the carbon monoxide generation reaction section 18. , and does not have the water vapor removal section 12 . Furthermore, unlike the third embodiment, the carburizing gas supply system 50 does not include the second supply section 9 .
  • the first supply section 8 supplies carbon dioxide to the separation gas on the downstream side of the separation section 17 in the gas flow path 20 . Then, the mixed gas in which the separation gas and the carbon dioxide supplied to the separation gas are mixed is introduced into the electrolytic reaction section 19 of the carbon dioxide conversion section 10 via the gas flow path 20 .
  • the reaction represented by the formula (6) is advanced by electrolysis, so that the carbon dioxide contained in the mixed gas, that is, the carbon dioxide contained in the separated gas and the dioxide supplied to the separated gas Produces carbon monoxide from carbon.
  • hydrogen is generated from the water vapor (water) contained in the mixed gas as the reaction represented by the formula (7) proceeds.
  • the amount of current in the electrolysis is controlled so that the carbon dioxide contained in the mixed gas is converted to carbon monoxide. is also used, so not all carbon dioxide is converted to carbon monoxide.
  • oxygen is generated from oxide ions by advancing the reaction shown in formula (8) by electrolysis.
  • the electrolytic reaction section 19 discharges the oxygen to the outside.
  • the mixed gas is converted into the converted gas by the reactions shown in the formulas (6) to (8).
  • the electrolysis reaction unit 19 is not particularly limited, but includes a solid oxide cell capable of co-electrolysis of water vapor and carbon dioxide.
  • the reforming reaction section 14 is arranged on the downstream side of the electrolytic reaction section 19 in the gas flow path 20, and the remainder of the exhaust gas and the converted gas after the separation gas is separated are represented by the formulas (4) and (5). A reformed gas that is reformed by the reaction is generated.
  • the carburizing gas supply system 50 and the carburizing system 100 according to the fourth embodiment are the same as those of the third embodiment except for the method of controlling the amount of carbon dioxide supplied in the first supply unit 8. is.
  • the functions of the second supply unit 9 and the carbon monoxide generation reaction unit 18 according to the third embodiment can be integrated into the electrolytic reaction unit 19, so the configuration can be simplified compared to the third embodiment. . Also, by controlling the amount of electric current in electrolysis, it becomes possible to control the reaction rate, which facilitates the control of the reaction.
  • the present invention is not limited to the embodiments. However, it is included in the technical scope of the present invention and includes various modifications.
  • the embodiments are described in detail in order to explain the present invention in an easy-to-understand manner, and are not necessarily limited to those having all the described configurations.
  • part of the configuration of one embodiment can be replaced with the configuration of another embodiment, and the configuration of another embodiment can be added to the configuration of one embodiment.

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  • Furnace Details (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)
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  • Waste-Gas Treatment And Other Accessory Devices For Furnaces (AREA)
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Abstract

Le but principal de la présente invention est de fournir un système d'alimentation en gaz de cémentation avec lequel il est possible de réduire la quantité d'émission de dioxyde de carbone, de réduire la quantité d'utilisation de nouveau gaz de cémentation, et de fournir une composition de gaz optimale en fonction de l'état dans un four.　Ce système d'alimentation en gaz de cémentation comprend : une unité d'évacuation de gaz qui évacue un gaz d'échappement d'un four à cémenter ; une première unité de mesure de débit qui mesure le débit du gaz d'échappement ; une première unité de mesure de concentration qui mesure la concentration de composants du gaz d'échappement ; une première unité d'alimentation qui fournit du dioxyde de carbone au gaz d'échappement ; une unité de commande qui commande la quantité d'alimentation du dioxyde de carbone sur la base du débit du gaz d'échappement et de la concentration des composants ; une unité de conversion de dioxyde de carbone qui génère un hydrocarbure ou du monoxyde de carbone à partir du dioxyde de carbone, et élimine l'eau ou l'oxygène ; et une unité d'alimentation en gaz de cémentation qui fournit, au four à cémenter, un gaz de cémentation régénéré contenant des composants dérivés de l'hydrocarbure généré ou du monoxyde de carbone généré.
PCT/JP2022/002544 2021-03-25 2022-01-25 Système d'alimentation en gaz de cémentation et système de cémentation Ceased WO2022201828A1 (fr)

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WO2025075128A1 (fr) * 2023-10-05 2025-04-10 学校法人トヨタ学園 Cylindre d'échappement et four de cémentation à gaz

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JP7781242B1 (ja) * 2024-10-15 2025-12-05 大同プラント工業株式会社 雰囲気炉および雰囲気制御方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002339017A (ja) * 2001-05-18 2002-11-27 Daido Steel Co Ltd 熱処理方法および熱処理装置
JP2017226893A (ja) * 2016-06-24 2017-12-28 大同特殊鋼株式会社 ガス供給システム

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002339017A (ja) * 2001-05-18 2002-11-27 Daido Steel Co Ltd 熱処理方法および熱処理装置
JP2017226893A (ja) * 2016-06-24 2017-12-28 大同特殊鋼株式会社 ガス供給システム

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025075128A1 (fr) * 2023-10-05 2025-04-10 学校法人トヨタ学園 Cylindre d'échappement et four de cémentation à gaz

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