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WO2023112845A1 - Dispositif de production et procédé de production d'un composé hydrocarboné - Google Patents

Dispositif de production et procédé de production d'un composé hydrocarboné Download PDF

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Publication number
WO2023112845A1
WO2023112845A1 PCT/JP2022/045408 JP2022045408W WO2023112845A1 WO 2023112845 A1 WO2023112845 A1 WO 2023112845A1 JP 2022045408 W JP2022045408 W JP 2022045408W WO 2023112845 A1 WO2023112845 A1 WO 2023112845A1
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WIPO (PCT)
Prior art keywords
temperature
unit
hydrocarbon
cathode
fuel synthesizing
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PCT/JP2022/045408
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English (en)
Japanese (ja)
Inventor
拓哉 北畠
暁 茂木
勉 樋口
祐之輔 中原
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Mitsui Kinzoku Co Ltd
Original Assignee
Mitsui Mining and Smelting Co Ltd
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Filing date
Publication date
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Publication of WO2023112845A1 publication Critical patent/WO2023112845A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C9/00—Aliphatic saturated hydrocarbons
    • C07C9/02—Aliphatic saturated hydrocarbons with one to four carbon atoms
    • C07C9/04—Methane
    • 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
    • C25B13/00—Diaphragms; Spacing elements
    • C25B13/04—Diaphragms; Spacing elements characterised by the material
    • C25B13/05—Diaphragms; Spacing elements characterised by the material based on inorganic materials
    • C25B13/07—Diaphragms; Spacing elements characterised by the material based on inorganic materials based on ceramics
    • 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
    • C25B15/021—Process control or regulation of heating or cooling
    • 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
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/25—Reduction
    • C25B3/26—Reduction of carbon dioxide
    • 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
    • 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
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
    • C25B9/23—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms comprising ion-exchange membranes in or on which electrode material is embedded

Definitions

  • the present invention relates to an apparatus and method for producing a hydrocarbon-based compound that synthesizes a hydrocarbon-based compound from H 2 O and CO 2 by energization, and in particular, production in which the temperature is raised by the heat generated during the synthesis of the hydrocarbon-based compound.
  • a hydrocarbon-based compound manufacturing apparatus that cools the apparatus and heats the excessively cooled manufacturing apparatus to suppress heat generation, thereby suppressing a decrease in conversion efficiency due to electrolysis of H 2 O and CO 2 ; It relates to a manufacturing method.
  • Patent Document 1 a system using a methanation reaction using CO 2 , which is a cause of global warming, as a raw material has been proposed (for example, Patent Document 1).
  • a water electrolysis system PCEC
  • proton conductive ceramics for example, Non-Patent Document 1
  • methane can be produced by simultaneously electrolyzing CO 2 on the cathode side.
  • the temperature should be 700° C. or less at normal pressure from the viewpoint of methanation reaction equilibrium, and 550° C. or less from the viewpoint of CO 2 conversion efficiency.
  • the temperature rises as the reaction progresses, and the methane production efficiency decreases.
  • the electrolysis efficiency of the PCEC will decrease, and the methane production efficiency will also decrease.
  • a manufacturing apparatus in producing a hydrocarbon compound such as methane in a PCEC co-electrolytic system, a manufacturing apparatus is provided without adding a dedicated cooling device or heating device in addition to the PCEC co-electrolytic system.
  • An object of the present invention is to provide an apparatus and method for producing a hydrocarbon-based compound that can efficiently suppress overheating and supercooling of the hydrocarbon-based compound and continue the efficient production of the hydrocarbon-based compound.
  • the present invention was invented to solve the problems in the prior art as described above, and the apparatus and method for producing a hydrocarbon compound of the present invention include those configured as follows. .
  • a hydrocarbon-based compound manufacturing apparatus for synthesizing a hydrocarbon-based compound from H 2 O and CO 2 by energization, an electrolytic cell having a fuel synthesis section including a cathode, a proton generation section including an anode, and an electrolyte membrane disposed between the cathode and the anode; an H 2 O supply unit that supplies H 2 O to the proton generation unit; a cathode gas supply unit that supplies a cathode gas containing CO 2 to the fuel synthesizing unit; an H 2 O preliminary temperature controller for adjusting the temperature of H 2 O supplied to the proton generator; a cathode gas preliminary temperature controller for adjusting the temperature of the cathode gas supplied from the cathode gas supplier; and the proton generator.
  • a temperature control system having at least one proton generating part temperature control part for controlling the temperature of the part; a fuel synthesizing unit temperature measuring unit for measuring the temperature of the fuel synthesizing unit; and a controller that controls the amount of heat generated by the temperature control system based on the temperature of the fuel synthesizing unit measured by the temperature measuring unit of the fuel synthesizing unit.
  • the fuel synthesizing unit temperature measuring unit measures the temperature difference between the inlet side temperature and the outlet side temperature of the fuel synthesizing unit, the temperature difference between the inlet side temperature of the fuel synthesizing unit and the temperature of the cathode, and the fuel synthesizing unit temperature.
  • the apparatus for producing a hydrocarbon-based compound according to any one of [1] to [3], wherein at least one of the outlet-side temperatures of the part is measured.
  • [5] further comprising a generated gas measuring unit for measuring the amount of generated gas generated in the fuel synthesizing unit;
  • the control unit According to any one of [1] to [4], the calorific value of the temperature control system is controlled based on the temperature of the fuel synthesizing unit and the amount of generated gas measured by the generated gas measuring unit. production equipment for hydrocarbon compounds.
  • [6] further comprising a hydrocarbon-based compound production rate measuring unit that measures the production rate R of the hydrocarbon-based compound produced in the fuel synthesizing unit with respect to the amount of CO 2 supplied from the cathode gas supply unit;
  • the control unit Any one of [1] to [5], wherein the calorific value of the temperature control system is controlled based on the temperature of the fuel synthesizing unit and the production rate R measured by the hydrocarbon compound production rate measuring unit.
  • a current-voltage measuring unit that measures at least one of a voltage value to the anode with respect to the cathode, a current value flowing between the cathode and the anode, and an electrical resistance value between the cathode and the anode; further prepared, The control unit Any one of [1] to [6], wherein the amount of heat generated by the temperature control system is controlled based on at least one of the voltage value, the current value, and the electrical resistance value measured by the current/voltage measurement unit. 2.
  • an electrolytic cell having a fuel synthesizing section including a cathode, a proton generating section including an anode, and an electrolyte membrane disposed between the cathode and the anode; an H 2 O supply unit that supplies H 2 O to the proton generation unit; a cathode gas supply unit that supplies a cathode gas containing CO 2 to the fuel synthesizing unit; an H 2 O preliminary temperature controller for adjusting the temperature of H 2 O supplied to the proton generator; a cathode gas preliminary temperature controller for adjusting the temperature of the cathode gas supplied from the cathode gas supplier; and the proton generator.
  • a temperature control system having at least one of a proton generating part and a temperature control part for adjusting the temperature of the part, and by energizing H 2 O and CO 2 to a hydrocarbon compound.
  • a method for producing a hydrocarbon compound that synthesizes A method for producing a hydrocarbon-based compound, wherein the calorific value of the temperature control system is controlled based on the temperature of the fuel synthesizing section.
  • the temperature of the fuel synthesizing section is the temperature difference between the inlet side temperature and the outlet side temperature of the fuel synthesizing section, the temperature difference between the inlet side temperature of the fuel synthesizing section and the temperature of the cathode, and the fuel synthesizing section.
  • the temperature control system Based on at least one of a voltage value to the anode with respect to the cathode, a current value flowing between the cathode and the anode, and an electrical resistance value between the cathode and the anode, the temperature control system
  • the temperature of at least one of the H 2 O supplied to the proton generation section, the cathode gas supplied from the cathode gas supply section, and the proton generation section is adjusted based on the temperature of the fuel synthesis section including the cathode.
  • FIG. 1 is a schematic diagram for explaining the configuration of a hydrocarbon-based compound production apparatus according to the present embodiment.
  • FIG. 1 is a schematic diagram for explaining the configuration of a hydrocarbon-based compound production apparatus according to the present embodiment. Note that in FIG. 1 , some lines indicating electrical connections with the control unit 60 are not shown in order to avoid complication of the drawing.
  • hydrocarbon-based compound an example of producing methane (CH 4 ) as a fuel (also referred to as a “hydrocarbon-based compound” in this specification) is described, but the present invention is directed to hydrocarbons such as methane and ethane.
  • manufacturing of hydrocarbon compounds consisting of carbon and hydrogen including alcohols such as methanol and ethanol, aldehydes such as formaldehyde and acetaldehyde, carboxylic acids such as formic acid and acetic acid, and ethers such as dimethyl ether. It can also be applied to devices and manufacturing methods.
  • the type of hydrocarbon compound to be produced can be selected, for example, by selecting the material of the cathode or adjusting the amounts of CO 2 and H 2 O supplied to the production apparatus. Hydrocarbon compounds can also be produced simultaneously.
  • the hydrocarbon-based compound manufacturing apparatus 10 of the present embodiment includes a fuel synthesizing section 20 including a cathode 22, a proton generating section 30 including an anode 32, and between the cathode 22 and the anode 32 an electrolytic cell 40 having an electrolyte membrane 42 disposed thereon.
  • the anode 32 and the cathode 22 are connected to a power source 50 and are configured such that current flows from the cathode 22 to the power source 50 and current flows from the power source 50 to the anode 32 .
  • the electrolyte membrane 42 is not particularly limited as long as it is a membrane that has the property of allowing ions to pass through mainly as charge carriers, and has the property of preventing an electrical short circuit between the anode 32 and the cathode 22.
  • Proton-conducting ceramics are preferably used as such a proton-conducting material.
  • An H 2 O supply unit 34 for supplying H 2 O to the proton generation unit 30 is connected to the proton generation unit 30, while a cathode containing CO 2 in the fuel synthesis unit 20 is connected to the fuel synthesis unit 20.
  • a cathode gas supply unit 24 for supplying gas is connected.
  • the cathode gas supplied from the cathode gas supply unit 24 is not particularly limited as long as it contains at least CO2 .
  • a mixed gas with an active gas, or a mixed gas with NOx or CO may be used. Alternatively, air may be used.
  • Pressure regulating valves 35 and 25 are provided on the H 2 O supply path 33 from the H 2 O supply section 34 to the proton generation section 30 and on the cathode gas supply path 23 from the cathode gas supply section 24 to the fuel synthesis section 20, respectively. is provided.
  • a check valve 36 is provided on the H 2 O supply path 33 from the H 2 O supply unit 34 to the proton generation unit 30 , and the H 2 O This prevents H 2 O from flowing back to the 2 O supply section 34 .
  • the hydrocarbon-based compound manufacturing apparatus 10 includes a carrier gas supply unit 38 that supplies a carrier gas that carries H 2 O supplied from the H 2 O supply unit 34 .
  • a pressure regulating valve 35 is also provided on the path from the carrier gas supply section 38 to the proton generating section 30 .
  • the amount of H 2 O supplied to the proton generating unit 30 can be determined using an analytical instrument or measuring instrument such as a gas chromatograph or a mass flow meter. can be accurately grasped. That is, it is possible to more accurately control the amount of H 2 O supplied from the H 2 O supply section 34 to the proton generation section 30 based on the values obtained from the above-mentioned analysis equipment and measuring instruments.
  • the fuel synthesizing section 20 is provided with a cathode gas temperature adjusting section 29
  • the proton generating section 30 is provided with an H 2 O temperature adjusting section 39 .
  • the cathode gas temperature control section 29 and the H 2 O temperature control section 39 generate heat to generate CO 2 and H 2 O. 2 O electrolysis efficiency is improved.
  • the hydrocarbon-based compound manufacturing apparatus 10 also includes a cathode gas preliminary temperature control unit 27 that controls the temperature of the cathode gas supplied from the cathode gas supply unit 24 to the fuel synthesis unit 20 .
  • a cathode gas preliminary temperature control unit 27 controls the temperature of the cathode gas supplied from the cathode gas supply unit 24 to the fuel synthesis unit 20 .
  • the temperature of the cathode gas is more preferably 100° C. or higher and 400° C. or lower, and still more preferably 300° C. or higher and 400° C. or lower.
  • the hydrocarbon-based compound manufacturing apparatus 10 of the present embodiment includes an H 2 O preliminary temperature control section 37 that controls the temperature of H 2 O supplied from the H 2 O supply section 34 to the proton generation section 30.
  • H 2 O preliminary temperature control section 37 controls the temperature of H 2 O supplied from the H 2 O supply section 34 to the proton generation section 30.
  • the H 2 O temperature control section 39, the H 2 O preliminary temperature control section 37, and the cathode gas preliminary temperature control section 27, which are the proton generating section temperature control sections, are referred to as a temperature control system.
  • the temperature control system includes the H 2 O temperature control unit 39, the H 2 O preliminary temperature control unit 37, and the cathode gas preliminary temperature control unit 27, but at least one of them is included. as long as it is
  • the produced gas containing the hydrocarbon compound produced in the fuel synthesizing section 20 is discharged from the outlet 20b of the fuel synthesizing section 20 .
  • the generated gas discharged from the outlet 20b of the fuel synthesizing unit 20 may contain, in addition to hydrocarbon compounds, CO 2 , CO, H 2 , H 2 O, etc. that have not undergone a generation reaction. .
  • the discharge part 30b may be provided at any position as long as the gas in the proton generation part 30 can be discharged. Note that H 2 O that has not been electrolyzed is also discharged from the discharge part. Also, although not shown, for example, a path for the discharged H 2 O to flow from the discharge portion 30b to the H 2 O supply portion 34 may be provided and circulated, so that H 2 O can be reused.
  • the fuel synthesizing section 20 is provided with a fuel synthesizing section temperature measuring section 21 for measuring the temperature of the fuel synthesizing section 20 .
  • the temperature of the fuel synthesizing section 20 measured by the fuel synthesizing section temperature measuring section 21 is output as an electric signal and transmitted to the control section 60 as will be described later.
  • the fuel synthesizing unit temperature measuring unit 21 is provided on the outlet 20b side of the fuel synthesizing unit 20, and the temperature of the generated gas discharged from the fuel synthesizing unit 20 is measured as the temperature of the fuel synthesizing unit 20.
  • the fuel synthesizing unit temperature measuring unit 21 is provided on both the inlet 20a side and the outlet 20b side of the fuel synthesizing unit 20, and the inlet side temperature (supplied cathode gas temperature) and the outlet side temperature (the temperature of the produced gas discharged) may be measured.
  • the fuel synthesizing unit temperature measuring unit 21 is provided on the inlet 20a side of the fuel synthesizing unit and on the surface of the cathode 22 to measure the temperature difference between the inlet side temperature (the temperature of the supplied cathode gas) and the temperature of the cathode 22. You may make it
  • the fuel synthesizing unit temperature measuring unit 21 and the temperature control system are electrically connected to each other. 60 , and the control unit 60 is configured to control the amount of heat generated by the temperature control system based on the output signal of the fuel synthesizing unit temperature measuring unit 21 .
  • the control unit 60 for example, a microcontroller having calculation means, storage means, input/output means, etc. can be used.
  • control unit 60 can be configured to acquire the H 2 O supply amount in real time from the electrically connected H 2 O supply unit 34 .
  • control unit 60 is electrically connected to the cathode gas supply unit 24, and can be configured to obtain the CO 2 supply amount in real time.
  • the amount of CO 2 supplied is determined by measuring the amount of CO 2 contained in the cathode gas using a known analyzer or measuring instrument. can be
  • control unit 60 is electrically connected to the carrier gas supply unit 38, acquires the carrier gas supply amount in real time, and based on the temperature of the fuel synthesis unit 20 measured by the fuel synthesis unit temperature measurement unit 21, By controlling the H 2 O supply amount supplied from the H 2 O supply unit 34 and the carrier gas supply amount supplied from the carrier gas supply unit 38, the supply amount of H 2 O supplied to the proton generation unit 30 is controlled. are doing.
  • the controller 60 controls the heat generation of the temperature control system based on the temperature of the fuel synthesizing unit 20 measured by the fuel synthesizing unit temperature measuring unit 21. control the amount.
  • the calorific value of the temperature control system is reduced.
  • the temperature of the fuel synthesizing section 20 becomes lower than the predetermined temperature range due to supercooling, for example, the heat generation amount of the temperature control system is increased.
  • the calorific value of the temperature control system is used as the standard value.
  • the "standard value" of the calorific value of the temperature control system means a calorific value at which the desired production efficiency of the hydrocarbon-based compound is obtained without reducing the electrolysis efficiency in the production of the hydrocarbon-based compound, It varies depending on the design, size, etc. of the manufacturing apparatus 10 .
  • the heating values of the H 2 O temperature control section 39, the H 2 O preliminary temperature control section 37, and the cathode gas preliminary temperature control section 27 may be individually controlled, or the H 2 O temperature control section 39, H The heating values of the 2 O preliminary temperature control section 37 and the cathode gas preliminary temperature control section 27 may be controlled to decrease or increase at the same time.
  • the heat generation amount of the temperature control system may be controlled based on the respective temperatures of the H 2 O temperature control section 39, the H 2 O preliminary temperature control section 37, and the cathode gas preliminary temperature control section 27.
  • the H 2 O temperature control section 39 , the H 2 O preliminary temperature control section 37 and the cathode gas preliminary temperature control section 27 may be controlled.
  • the predetermined temperature range can be appropriately set from the viewpoint of methanation reaction equilibrium, CO 2 conversion efficiency, and the like.
  • the temperature range can be set to 300° C. or higher and 700° C. or lower. It is more preferably 330°C or higher and 650°C or lower, and still more preferably 350°C or higher and 600°C or lower.
  • the amount of heat generated by the temperature control system By controlling the amount of heat generated by the temperature control system in this way, when the temperature of the manufacturing apparatus 10 rises, the amount of heat generated by the temperature control system is suppressed, thereby cooling the entire manufacturing apparatus 10. On the other hand, when the temperature of the manufacturing apparatus 10 drops, the entire manufacturing apparatus 10 can be heated by increasing the amount of heat generated by the temperature control system. By controlling in this way, it is possible to suppress a decrease in the electrolysis efficiency of CO 2 at the cathode 22 and a decrease in the production efficiency of methane, and to continue the efficient production of methane.
  • the hydrocarbon-based compound production apparatus 10 of the present embodiment has a production rate R of the hydrocarbon-based compound in the fuel synthesizing unit 20 with respect to the amount of CO 2 supplied from the cathode gas supply unit 24.
  • a hydrocarbon-based compound generation rate measuring unit 62 for measurement is provided.
  • the hydrocarbon-based compound production rate measuring unit 62 is provided in the outlet side pipe 26 of the fuel synthesizing unit 20 .
  • the hydrocarbon-based compound production rate measurement unit 62 is electrically connected to the control unit 60, and acquires the CO 2 supply amount from the cathode gas supply unit 24 via the control unit 60, whereby the CO 2 Calculates the production rate R of hydrocarbon-based compounds with respect to the supply amount.
  • the calculated generation rate R is transmitted to the control section 60 as an electrical signal.
  • the hydrocarbon-based compound production rate measurement unit 62 calculates the production rate R from the ratio of the produced hydrocarbon-based compound production amount to the CO 2 supply amount, and outputs the calculated production rate R to the control unit 60 .
  • the amount (volume) of hydrocarbon-based compounds produced can be measured using a known measuring device such as a gas chromatograph . It can also be calculated using a value.
  • the control unit 60 controls the calorific value of the temperature control system based on the temperature of the fuel synthesizing unit 20 and the production rate R obtained from the hydrocarbon-based compound production rate measuring unit 62 . That is, when the generation rate R is equal to or less than a predetermined generation rate threshold value, it is determined that the fuel synthesizing unit 20 is overheated or supercooled and the generation efficiency of the hydrocarbon compound is reduced, and the calorific value of the temperature control system is reduced. Lower or raise. On the other hand, if the generation rate R exceeds the predetermined generation rate threshold, control by the control unit 60 is not performed.
  • the production rate threshold value can be appropriately set, for example, based on the design of heat storage and heat release of the hydrocarbon-based compound manufacturing apparatus 10 .
  • the hydrocarbon-based compound manufacturing apparatus 10 of the present embodiment includes a product gas separation section 64 that separates only methane from the product gas in the fuel synthesizing section 20 .
  • the product gas separation unit 64 is provided downstream of the hydrocarbon-based compound production rate measurement unit 62 in the outlet pipe 26 of the fuel synthesis unit 20 .
  • the methane separated by the generated gas separation section 64 is recovered and stored in the CH 4 recovery section 66 .
  • the generated gas separation unit 64 is configured to separate only methane, but the generated gas other than methane after separation can be discharged as it is. It is also possible to separate each component and reuse CO 2 and H 2 O contained in the generated gas.
  • the hydrocarbon-based compound manufacturing apparatus 10 of the present embodiment includes a generated gas measurement unit 68 that measures the amount of generated gas generated in the fuel synthesizing unit 20, as shown in FIG.
  • the generated gas measurement unit 68 is provided upstream of the generated gas separation unit 64 in the outlet pipe 26 of the fuel synthesizing unit 20 .
  • the amount of generated gas measured by the generated gas measurement unit 68 is transmitted to the control unit 60 as an electric signal, and the control unit 60 determines the temperature based on the amount of generated gas generated and the temperature of the fuel synthesizing unit 20. It controls the amount of heat generated by the control system.
  • control unit 60 determines that the CO 2 electrolysis efficiency at the cathode 22 and the methane production efficiency have decreased, that is, fuel synthesis It is determined that the unit 20 is overheated or supercooled, and control is performed to reduce the amount of heat generated by the temperature control system.
  • the hydrocarbon-based compound production apparatus 10 of the present embodiment also includes a CH 4 measurement unit 65 that measures the amount of methane produced in the fuel synthesis unit 20 .
  • the CH 4 measurement unit 65 is provided downstream of the product gas separation unit 64 and upstream of the CH 4 recovery unit 66 in the outlet pipe 26 of the fuel synthesis unit 20 .
  • the hydrocarbon-based compound manufacturing apparatus 10 of the present embodiment includes a voltage measuring section 52 (current-voltage measuring section) that measures the voltage value of the anode 32 with respect to the cathode 22 .
  • the voltage measurement unit 52 is electrically connected to the control unit 60, and the voltage value of the anode 32 with respect to the cathode 22 measured by the voltage measurement unit 52 is transmitted to the control unit 60 as an electric signal.
  • the control unit 60 controls the amount of heat generated by the temperature control system based on the voltage value obtained from the voltage measurement unit 52. That is, when the voltage value becomes lower than the predetermined voltage range, it is determined that the methane production reaction has progressed and the temperature of the fuel synthesizing section 20 has risen, and the amount of heat generated by the temperature control system is reduced. On the other hand, when the voltage value exceeds the predetermined voltage range, it is determined that the methane production reaction is not progressing sufficiently and the temperature of the fuel synthesizing section 20 is decreasing, and the calorific value of the temperature control system is reduced. raise.
  • the predetermined voltage range can be appropriately set based on the design of heat storage and heat dissipation of the hydrocarbon-based compound manufacturing apparatus 10 .
  • the current value flowing between the cathode 22 and the anode 32 is kept constant, and in order to measure the voltage value of the anode 32 with respect to the cathode 22, the voltage measurement unit 52 is used as the current/voltage measurement unit.
  • the voltage measurement unit 52 can also be used as a current measurement unit for measuring the value of the current flowing between the cathode 22 and the anode 32.
  • it may be an electrical resistance measuring unit that measures the electrical resistance value between the cathode 22 and the anode 32 .
  • the value of the current flowing through the power supply 50 can also be used as the value of the current flowing between the cathode 22 and the anode 32 .
  • the electrical resistance value between the cathode 22 and the anode 32 the electrical resistance value between the surface of the cathode 22 on the side of the fuel synthesizing unit 20 and the surface of the anode 32 on the side of the proton generating unit 30 is measured. preferably.
  • control unit 60 controls the amount of heat generated by the temperature control system based on the current value and the electrical resistance value.
  • the fuel synthesizing section 20 may be provided with a gas diffusion layer or a hydrogenation catalyst layer. With such a configuration, the production efficiency of hydrocarbon-based compounds can be improved.
  • manufacturing device 20 fuel synthesizing unit 20a fuel synthesizing unit inlet 20b fuel synthesizing unit outlet 21 fuel synthesizing unit temperature measuring unit 22 cathode 23 cathode gas supply path 24 cathode gas supply unit 25 pressure control valve 26 outlet pipe 27 cathode gas preliminary temperature control Part 29 Cathode gas temperature control part 30 Proton generation part 30b Discharge part (proton generation part outlet) 32 anode 33 H 2 O supply path 34 H 2 O supply unit 35 pressure control valve 36 check valve 37 H 2 O preliminary temperature control unit 38 carrier gas supply unit 39 H 2 O temperature control unit 40 electrolytic cell 42 electrolyte membrane 50 power supply 52 voltage measurement unit 60 control unit 62 hydrocarbon compound production rate measurement unit 64 generated gas separation unit 65 CH 4 measurement unit 66 CH 4 recovery unit 68 generated gas measurement unit

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  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

Le problème décrit par la présente invention est de fournir un dispositif de production et un procédé de production pour un composé hydrocarboné avec lequel la surchauffe ou le surrefroidissement du dispositif de production sont efficacement supprimés sans utiliser de dispositif de refroidissement ou de dispositif de chauffage dédié et la production efficace d'un composé hydrocarboné peut être poursuivie, lors de la production d'un composé hydrocarboné tel que le méthane dans un système de co-électrolyse PCEC.　La solution selon l'invention porte sur un dispositif de production, qui est destiné à un composé hydrocarboné et avec lequel un composé hydrocarboné est synthétisé à partir d'H2O et de CO2 par énergisation, comprenant : un réservoir électrolytique qui comporte une unité de synthèse de combustible qui comprend une cathode, une unité de génération de protons qui comprend une anode et une membrane électrolytique qui se situe entre la cathode et l'anode ; une unité d'alimentation en H2O qui fournit de l'H2O à l'unité de génération de protons ; une unité d'alimentation en gaz de cathode qui fournit un gaz de cathode contenant du CO2 à l'unité de synthèse de combustible ; un système de réglage de température qui possède au moins l'une parmi une unité de réglage de température préliminaire d'H2O qui ajuste la température de l'H2O fourni à l'unité de génération de protons, une unité de réglage de température préliminaire de gaz de cathode qui ajuste la température du gaz de cathode fourni par l'unité d'alimentation en gaz de cathode et une unité de réglage de température d'unité de génération de protons qui ajuste la température de l'unité de génération de protons ; une unité de mesure de température d'unité de synthèse de combustible qui mesure la température de l'unité de synthèse de combustible ; et une unité de régulation qui régule la quantité de chaleur générée par le système de réglage de température sur la base de la température de l'unité de synthèse de combustible mesurée par l'unité de mesure de température d'unité de synthèse de combustible.
PCT/JP2022/045408 2021-12-16 2022-12-09 Dispositif de production et procédé de production d'un composé hydrocarboné Ceased WO2023112845A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20110113003A (ko) * 2010-04-08 2011-10-14 전남대학교산학협력단 메탄-산소 발생 장치 및 이를 이용한 이산화탄소와 물로부터 메탄과 산소를 제조하는 방법
JP2013119556A (ja) * 2011-12-06 2013-06-17 Mitsubishi Heavy Ind Ltd 燃料製造方法及び燃料製造装置
WO2019048016A1 (fr) * 2017-09-07 2019-03-14 Danmarks Tekniske Universitet Procédé et appareil de production de méthane

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KR20110113003A (ko) * 2010-04-08 2011-10-14 전남대학교산학협력단 메탄-산소 발생 장치 및 이를 이용한 이산화탄소와 물로부터 메탄과 산소를 제조하는 방법
JP2013119556A (ja) * 2011-12-06 2013-06-17 Mitsubishi Heavy Ind Ltd 燃料製造方法及び燃料製造装置
WO2019048016A1 (fr) * 2017-09-07 2019-03-14 Danmarks Tekniske Universitet Procédé et appareil de production de méthane

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Title
XIE KUI, ZHANG YAOQING, MENG GUANGYAO, IRVINE JOHN T. S.: "Electrochemical reduction of CO2 in a proton conducting solid oxide electrolyser", JOURNAL OF MATERIALS CHEMISTRY, ROYAL SOCIETY OF CHEMISTRY, GB, vol. 21, no. 1, 1 January 2011 (2011-01-01), GB , pages 195 - 198, XP093071464, ISSN: 0959-9428, DOI: 10.1039/C0JM02205E *

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