WO2023003029A1 - 二酸化炭素回収システム - Google Patents
二酸化炭素回収システム Download PDFInfo
- Publication number
- WO2023003029A1 WO2023003029A1 PCT/JP2022/028267 JP2022028267W WO2023003029A1 WO 2023003029 A1 WO2023003029 A1 WO 2023003029A1 JP 2022028267 W JP2022028267 W JP 2022028267W WO 2023003029 A1 WO2023003029 A1 WO 2023003029A1
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- WIPO (PCT)
- Prior art keywords
- carbon dioxide
- gas
- passage
- electrolyte
- pressure
- Prior art date
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- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 325
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 318
- 238000011084 recovery Methods 0.000 title claims abstract description 44
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Images
Classifications
-
- 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
- B01D53/26—Drying gases or vapours
-
- 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
- B01D53/32—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 by electrical effects other than those provided for in group B01D61/00
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
-
- 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
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C9/00—Aliphatic saturated hydrocarbons
- C07C9/02—Aliphatic saturated hydrocarbons with one to four carbon atoms
- C07C9/06—Ethane
-
- 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
- C25B1/02—Hydrogen or oxygen
-
- 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
- C25B3/20—Processes
- C25B3/25—Reduction
- C25B3/26—Reduction of carbon dioxide
Definitions
- the present invention relates to a carbon dioxide recovery system.
- Patent Document 1 discloses that carbon dioxide such as ethylene (C 2 H 4 ), methane (CH 4 ), methanol (CH 3 OH), and ethanol (C 2 H 5 OH) is produced by an electrolytic reduction reaction of carbon dioxide (CO 2 ).
- a carbon dioxide electrolyser is disclosed that produces one or more hydrocarbons.
- a carbon dioxide electrolyzer can be applied to a carbon dioxide recovery system that separates and recovers carbon dioxide from gas.
- carbon dioxide is reduced at the cathode to produce hydrocarbons such as ethylene. Since the hydrocarbons produced at the cathode are discharged from the carbon dioxide electrolyzer together with unreacted carbon dioxide, it is necessary to separate the carbon dioxide in a subsequent step.
- One of the separation methods is the cryogenic separation method.
- carbon dioxide is cooled at a pressure of several tens of atmospheres, which is the same as in existing ethylene plants, it changes from a gas to a solid, making it more difficult to handle than a liquid, reducing the efficiency of recovery and reuse. be.
- Another separation method is to have the amine absorb carbon dioxide. However, in this method, the amine must be heated when recovering the carbon dioxide from the amine, which poses a problem of poor energy efficiency.
- an object of the present invention is to improve energy efficiency in a carbon dioxide recovery system.
- one aspect of the present invention is a carbon dioxide recovery system (1), wherein a gas containing carbon dioxide is supplied, and the carbon dioxide is electrolytically reduced to produce hydrocarbons, carbon monoxide, , and an electrolytic reduction device (2) that generates a mixed gas containing at least a product gas containing at least one of hydrogen and unreacted carbon dioxide, and a carbon dioxide separation device (3) that separates carbon dioxide from the mixed gas.
- the carbon dioxide separator comprises a first gas diffusion electrode (51) that is a cathode, a second gas diffusion electrode (52) that is an anode, the first gas diffusion electrode and the second gas diffusion electrode (52).
- the electrolytic reduction device uses carbon dioxide separated from the mixed gas in the carbon dioxide separation device as part of the raw material.
- carbon dioxide is separated from the mixed gas in a gaseous state, so it is suitable for recovery and reuse of carbon dioxide.
- the carbon dioxide separator using electrochemistry can separate carbon dioxide from the mixed gas with less energy than the separation method using amine. Thereby, energy efficiency can be improved in the carbon dioxide recovery system.
- water and hydrocarbons can be efficiently separated from the produced gas. Further, even if water is mixed in the generated gas in the electrolytic reduction device or the carbon dioxide separation device, the water is separated in the subsequent water removal device.
- the combustion furnace (6) is provided for burning at least part of the off-gas, which is the generated gas from which hydrocarbons have been separated in the generated gas separation device, and the moisture removal device adsorbs water and An adsorption step of releasing the generated gas from which water has been separated and a desorption step of receiving heat generated in the combustion furnace and releasing the water adsorbed in the adsorption step may be performed.
- the heat of combustion of combustible gases such as hydrogen and carbon monoxide contained in the generated gas can be used to perform the desorption process of the moisture removal device, improving energy efficiency.
- the first gas-liquid separator (133) for separating liquefied water from the water-containing gas released in the desorption step of the water remover; and a circulation passageway (116) for returning the separated gas to the moisture removal device, the circulation passageway being arranged for heat exchange with the combustion furnace.
- the heat generated in the combustion furnace can be used to perform the desorption step of the moisture removal device.
- a part of the generated gas from which water has been separated in the moisture removal device may be supplied to the circulation passage.
- part of the generated gas can be used to supply the heat of the combustion furnace to the moisture removal device.
- the above aspect may have an exhaust gas passage (151) for supplying exhaust gas containing carbon dioxide and water generated in the combustion furnace to the electrolytic reduction.
- the carbon dioxide and water generated in the combustion furnace can be used as part of the raw materials for producing hydrocarbons, carbon monoxide, and the like.
- two of the water removal devices (4A, 4B) are provided in parallel, and when one of the water removal devices is performing the adsorption step, the other water removal device performs the desorption steps may be performed.
- the carbon dioxide separation device includes a carbon dioxide circulation passage (71) connected to the inlet and outlet of the second chamber of the carbon dioxide separation device, and the carbon dioxide circulation passage and the electrolytic reduction device.
- a product gas outlet passage (64, 66) connected to the outlet of the first chamber of the carbon dioxide separator, and an electrolyte supply passage (81) connected to the inlet of the liquid chamber, and , and an electrolyte tank (82) connected to the outlet of the liquid chamber via a first electrolyte return passage (87).
- carbon dioxide after increasing the pressure of carbon dioxide in the carbon dioxide circulation passage, carbon dioxide can be supplied to the electrolytic reduction device through the carbon dioxide return passage.
- a second gas-liquid separator (72) provided in the carbon dioxide circulation passage, and a second electrolyte return passage (72) for transferring the liquid separated in the second gas-liquid separator to the electrolyte tank 95
- a first pressure control valve (76) provided in the carbon dioxide return passage
- a second pressure control valve (68) provided in the mixed gas inlet passage or the produced gas outlet passage
- the electrolysis A third pressure control valve (flow rate control valve) (84) provided in the liquid supply passage or the first electrolyte return passage, and a first pressure sensor (PS1) for detecting the pressure in the first chamber as the first pressure.
- PS1 first pressure sensor
- a second pressure sensor for detecting the pressure in the second chamber as a second pressure
- a third pressure sensor for detecting the pressure in the liquid chamber as a third pressure
- a control device for controlling the first pressure control valve, the second pressure control valve, and the third pressure control valve so that the pressure is equal to or higher than the third pressure, and the third pressure is equal to or higher than the second pressure.
- the electrolytic solution that has leaked into the carbon dioxide circulation passage can be returned to the electrolytic solution tank.
- the fourth pressure control valve (69) provided downstream of the first pressure control valve in the produced gas outlet passage, and the fourth pressure control valve (69) in the top portion of the electrolyte tank and the produced gas outlet passage.
- the control device has a gas return passage (97) connecting a portion upstream of the 4 pressure control valve, and a fourth pressure sensor (PS4) for detecting the pressure of the electrolyte tank as a fourth pressure.
- PS4 fourth pressure sensor
- the gas remaining at the top of the electrolyte tank can be returned to the generated gas outlet passage through the gas return passage.
- the hydrocarbon may contain at least one of methane and ethylene.
- At least one of methane, ethylene, and carbon monoxide can be produced from carbon dioxide.
- the compound that adsorbs and desorbs protons with oxidation-reduction may be an organic compound having an oxidation-reduction potential of -1.0 V to 1.0 V based on the standard hydrogen electrode potential at pH 7.
- the compound that adsorbs and desorbs protons with oxidation-reduction may be a quinone-based compound.
- carbon dioxide can be efficiently separated.
- a carbon dioxide recovery system (1) which is supplied with a gas comprising carbon dioxide and electrolytically reduces the carbon dioxide to produce at least one of hydrocarbons, carbon monoxide and hydrogen and an electrolytic reduction device (2) for generating a mixed gas containing at least unreacted carbon dioxide and a generated gas containing
- the carbon separation device has a carbon dioxide gas absorption part (401 ), an electrolyte membrane (416A), and a cathode (416B) and an anode (416C) provided on both sides of said electrolyte membrane and connected to a power supply (419), by means of a membrane electrode assembly (416), the cathode chamber ( 417) and an electrochemical cell (402) partitioned into an anode chamber (418), a first passage (403) for flowing the electrolytic solution from the carbon dioxide gas absorption part to the anode chamber, and a second passage (404) for flowing the electrolyte from the cathode chamber to the cathode chamber; a third passage (405) for
- carbon dioxide is separated from the mixed gas in a gaseous state, so it is suitable for recovery and reuse of carbon dioxide.
- the carbon dioxide separator using electrochemistry can separate carbon dioxide from the mixed gas with less energy than the separation method using amine. Thereby, energy efficiency can be improved in the carbon dioxide recovery system.
- the carbon dioxide gas absorbing part includes a housing (431) that extends vertically and stores the electrolytic solution at the bottom, and a gas inlet ( 411), a gas outlet (412) provided at the upper end of the housing for discharging the mixed gas, a nozzle (432) provided at the upper portion of the housing for injecting the electrolyte, and the A fourth passage (433) for supplying the electrolyte stored in the bottom to the nozzle, and a fourth passage (433) provided between the gas inlet and the nozzle in the housing for temporarily supplying the electrolyte supplied from the nozzle.
- a first flow control valve (436A) is provided in the third passage, and a second flow control valve (436B) is provided in the fourth passage closer to the bottom of the housing than the third passage.
- the power source, the first flow control valve, and the second flow control valve are controlled by a control device (7), and the pH of the electrolyte stored in the bottom of the housing is set to pH 1, and the pH of the electrolyte in the fourth passage is If the pH of the electrolytic solution flowing through the nozzle side of the third passage is pH 2, the pH of the electrolytic solution flowing through the third passage is pH 3, and the pH of the electrolytic solution flowing through the first passage is pH 4, , the control device may control the power supply, the first flow control valve, and the second flow control valve to satisfy pH3 ⁇ pH2 ⁇ pH1 ⁇ pH4 ⁇ 5.5.
- the energy efficiency can be improved in the carbon dioxide recovery system.
- the carbon dioxide recovery system 1 has an electrolytic reduction device 2 and a carbon dioxide separation device 3 as main components.
- the carbon dioxide recovery system 1 further includes a moisture removal device 4 , a product gas separation device 5 and a combustion furnace 6 .
- the carbon dioxide recovery system 1 also has a control device 7 that controls each device, a flow rate control valve, etc., which will be described later.
- the control device 7 has a processor, a memory, and a storage device that stores programs, and controls each device by executing the programs.
- the electrolytic reduction device 2 supplies a gas containing carbon dioxide and electrolytically reduces the carbon dioxide, thereby reducing at least unreacted carbon dioxide and a produced gas containing at least one of hydrocarbon, carbon monoxide and hydrogen. to generate a gas mixture containing The mixed gas is discharged from the cathode 16 side of the electrolytic reduction device 2 .
- carbon dioxide is reduced to produce ethylene as the main product.
- a product containing by-products such as carbon monoxide, methane, and hydrogen is obtained.
- the electrolytic reduction apparatus 2 is a three-chamber type having a cathode gas chamber and a catholyte chamber partitioned by a cathode, which is a gas diffusion electrode, and an anolyte chamber partitioned from the catholyte chamber by a separator and in which an anode is arranged. or an electrolytic reduction device using a membrane electrode assembly (MEA) in which an electrolyte membrane is sandwiched between a cathode and an anode.
- MEA membrane electrode assembly
- the electroreduction device 2 has an electrolysis cell 14 with a cathode compartment 11 and an anode compartment 12 separated from each other by a membrane electrode assembly 10 .
- the membrane electrode assembly 10 has an electrolyte membrane 15 , a cathode 16 provided on one side of the electrolyte membrane 15 , and an anode 17 provided on the other side of the electrolyte membrane 15 .
- Gaseous carbon dioxide is supplied to the cathode chamber 11 .
- An anolyte is supplied to the anode chamber 12 .
- Cathode 16 and anode 17 are connected to DC power supply 19 .
- An anolyte is an aqueous solution in which an electrolyte is dissolved.
- the electrolyte includes at least one of potassium, sodium, lithium, or compounds thereof.
- the electrolyte may include, for example, at least one selected from the group consisting of LiOH, NaOH, KOH, Li2CO3 , Na2CO3 , K2CO3 , LiHCO3 , NaHCO3 , and KHCO3 .
- the electrolyte membrane 15 is made of a proton conductor that allows protons to pass through.
- the electrolyte membrane 15 is, for example, a solid polymer electrolyte membrane, preferably a fluororesin-based cation exchange resin membrane having sulfonic acid groups.
- the cathode 16 is a gas diffusion electrode. Cathode 16 is permeable to gases including carbon dioxide.
- the cathode 16 may be formed by forming a water-repellent film such as polytetrafluoroethylene on the surface of a porous conductive substrate such as carbon paper, carbon felt, or carbon cloth.
- the conductive base material is connected to the negative electrode of the DC power supply 19 and is supplied with electrons.
- a catalyst is supported on the cathode 16 .
- the catalyst may be a known carbon dioxide reduction catalyst, such as a group 11 element such as copper, a group 12 element such as zinc, a group 13 element such as gallium, a group 14 element such as germanium, or any of these At least one metal compound is included.
- Metal compounds include at least one of oxides, sulfides, and phosphides.
- the catalyst is preferably one suitable for reducing carbon dioxide to produce ethylene, e.g. copper or a copper compound with metals of group 11, group 12, group 13 and group 14 elements, and metal compounds thereof are preferably used.
- the anode 17 is made of, for example, metal materials such as titanium, nickel, molybdenum, platinum, gold, silver, copper, iron, lead, or metal alloy materials thereof, carbon-based materials such as carbon, or conductive ceramics.
- the shape of the anode 17 may be a plate with multiple openings, a mesh, and a porous body.
- the anode 17 carries an oxygen generating catalyst such as platinum or iridium.
- the DC power supply 19 converts electric power obtained from thermal power generation, nuclear power generation, photovoltaic power generation, wind power generation, hydroelectric power generation, etc. into direct current as necessary and supplies it to the cathode 16 and the anode 17 . From the viewpoint of reducing carbon dioxide emissions, it is preferable to use power obtained from solar power generation, wind power generation, hydraulic power generation, or the like using natural energy (renewable energy) as the DC power supply 19 .
- a DC power supply 19 applies a voltage to the anode 17 so that the cathode 16 has a negative potential.
- the DC power supply 19 preferably obtains the potential of the cathode 16 using a reference electrode and controls the applied voltage so that the potential of the cathode 16 is within a predetermined range.
- the cathode chamber 11 has an inlet 24 and an outlet 25 . As shown in FIGS. 1 and 2, inlet 24 of cathode chamber 11 is connected to carbon dioxide supply source 27 via first supply passage 26 .
- the carbon dioxide supply source 27 is not particularly limited as long as it can supply carbon dioxide gas, and is preferably a storage tank or the like.
- An outlet 25 of the cathode chamber 11 is connected via a gas circulation passage 28 to a first supply passage 26 .
- a flow control valve 29 is provided between the carbon dioxide supply source 27 and the first supply passage 26 . The flow control valve 29 controls the flow rate of carbon dioxide gas supplied from the carbon dioxide supply source 27 to the first supply passage 26 .
- the anode chamber 12 has an inlet 31 and an outlet 32 .
- Inlet 31 of anode chamber 12 is connected to water supply 34 via second supply passage 33 .
- a water supply source 34 supplies liquid water to the second supply passage 33 .
- An outlet 32 of the anode chamber 12 is connected to a second supply passage 33 via an anolyte circulation passage 35 .
- a flow control valve 36 is provided between the water supply source 34 and the second supply passage 33 .
- the flow control valve 36 controls the flow rate of liquid water supplied from the water supply source 34 to the second supply passage 33 .
- the second supply passage 33 is provided with a flow rate sensor S12 for measuring the flow rate of water flowing therein.
- the gas circulation passage 28 is provided with a gas circulation flow control device 38 that discharges part of the gas circulating inside.
- An outlet of the gas circulation flow control device 38 is connected to the cathode outlet passage 39 .
- the gas circulation flow control device 38 regulates the flow rate and pressure of the gas circulating through the gas circulation passage 28 and the cathode chamber 11 by discharging the gas to the cathode outlet passage 39 .
- a gas-liquid separation device 41 is provided in the anode fluid circulation passage 35 .
- the gas-liquid separator 41 separates the gas from the anolyte and delivers the gas to the anode outlet passage 42 .
- the anode fluid circulation passage 35 may be provided with an electrolyte concentration control device 43 for adjusting the electrolyte concentration of the anode fluid within a predetermined range.
- the electrolyte concentration control device 43 includes a sensor for detecting the electrolyte concentration of the anolyte, an electrolyte supply device for supplying new anolyte having a predetermined concentration, and a drain device for discharging a part of the circulating anolyte. good.
- Carbon dioxide in the cathode chamber 11 diffuses inside the cathode 16 and is reduced (see chemical formula (1)). This yields a product gas containing ethylene as the main product and by-products such as methane, hydrogen, carbon monoxide and formic acid.
- the generated gas is mixed with unreacted carbon dioxide in the cathode chamber 11 to form a mixed gas.
- the gas mixture may contain water and hydrocarbons such as propane and butane.
- the main components of the mixed gas are ethylene and carbon dioxide.
- the produced gas containing the product produced by the reduction reaction of carbon dioxide and unreacted carbon dioxide circulates through the gas circulation passage 28 and is sent out from the gas circulation flow control device 38 to the cathode outlet passage 39 .
- gaseous oxygen is separated from the anolyte by a gas-liquid separator 41 in the anolyte circulation passage 35 and delivered to the anode outlet passage 42 .
- the catalyst supported on the cathode 16 and the potential of the cathode 16 are preferably set so that the Faraday efficiency for ethylene production at the cathode 16 is 30% or more, preferably 50% or more.
- Faradaic efficiency is defined as the ratio of the current that contributed to the production of each product to the total current that flowed through the electrolytic cell 14 .
- the catalyst supported on the cathode 16 is preferably selected so that the selectivity for ethylene production at the cathode 16 is 30% or more.
- the gas flowing through the anode outlet passage 42 is mainly oxygen. In some cases, the gas flowing through the anode outlet passage 42 is mixed with carbon dioxide.
- the mixed gas discharged from the cathode outlet passage 39 of the electrolytic reduction device 2 is supplied to the carbon dioxide separation device 3 .
- the carbon dioxide separator 3 separates carbon dioxide from the mixed gas.
- the carbon dioxide separator 3 includes a first gas diffusion electrode 51 as a cathode, a second gas diffusion electrode 52 as an anode, and a first gas diffusion electrode 51 and a second gas diffusion electrode 52.
- a liquid chamber 53 is formed between the liquid chambers and is supplied with an electrolytic solution containing a compound that adsorbs and desorbs protons as a result of oxidation and reduction. and a second chamber 55 separated from the liquid chamber 53 by the second gas diffusion electrode 52 and through which carbon dioxide separated from the produced gas flows.
- the carbon dioxide separator 3 includes a first unit in which the second gas diffusion electrode 52, the liquid chamber 53, and the first gas diffusion electrode 51 are arranged in this order, the first gas diffusion electrode 51, the liquid chamber 53, It has a stack 59 in which a plurality of second units arranged in order of the second gas diffusion electrodes 52 are alternately laminated with a space therebetween.
- a first chamber 54 is formed between two adjacent first gas diffusion electrodes 51
- a second chamber 55 is formed between two adjacent second gas diffusion electrodes 52 .
- Each of the first gas diffusion electrode 51 and the second gas diffusion electrode 52 has a porous conductor.
- the porous conductor preferably has a large specific surface area in order to increase the reaction area.
- the specific surface area of the porous conductor is 1 m 2 /g or more, more preferably 100 m 2 /g or more, still more preferably 500 m 2 /g or more in BET adsorption measurement.
- the surface resistance of the porous conductor is preferably as low as possible, and is 1 k ⁇ / ⁇ or less, more preferably 200 ⁇ / ⁇ or less.
- the porous conductor may be, for example, a carbon sheet, carbon cloth, or carbon paper.
- the first gas diffusion electrode 51 and the second gas diffusion electrode 52 are preferably placed as close to each other as possible without contacting each other.
- a separator may be inserted between the first gas diffusion electrode 51 and the second gas diffusion electrode 52 .
- the separator has insulating properties and is permeable to the electrolytic solution.
- the separator may be selected from, for example, polyolefin porous membranes represented by polyethylene and polypropylene, polyester, aliphatic polyamide, aromatic polyamide porous membranes and non-woven fabrics, and the like.
- the plurality of first gas diffusion electrodes 51 are connected to the negative electrode of the DC power source 61
- the plurality of second gas diffusion electrodes 52 are connected to the positive electrode of the DC power source 61 .
- the cathode outlet passage 39 of the electrolytic reduction device 2 is connected to the inlet of each first chamber 54 via the mixed gas inlet passage 62 .
- a downstream portion of the mixed gas inlet passage 62 branches corresponding to each of the first chambers 54 .
- a blower 63 is provided in the upstream portion of the mixed gas inlet passage 62 to send out the generated gas toward the first chambers 54 .
- Each outlet of each first chamber 54 is connected to a first vessel 65 via a plurality of first generated gas outlet passages 64 .
- the first vessel 65 is connected to a second product gas outlet passage 66 .
- the generated gas discharged from each first chamber 54 passes through one of the plurality of first generated gas outlet passages 64, the first vessel 65, and the second generated gas outlet passage 66, and exits the carbon dioxide separator 3. Ejected.
- the second generated gas outlet passage 66 is provided with a pressure control valve 68 and a pressure control valve 69 in order from the first vessel 65 side.
- Each outlet of each first chamber 54 may be positioned above each inlet of each first chamber 54 .
- each second chamber 55 The inlet and outlet of each second chamber 55 are connected by a carbon dioxide circulation passage 71 .
- Each outlet of each second chamber 55 is preferably arranged below each inlet of each second chamber 55 .
- a second vessel 72 , a blower 73 , and a third vessel 74 are provided in this order from the outlet side to the inlet side of the second chamber 55 in the carbon dioxide circulation passage 71 .
- Carbon dioxide gas mainly flows through each of the second chambers 55 and the carbon dioxide circulation passage 71 .
- the second vessel 72 functions as a gas-liquid separator.
- the bottom of the second vessel 72 is arranged below each outlet of each second chamber 55 , and the carbon dioxide circulation passage 71 descends from each outlet of each second chamber 55 toward the second vessel 72 . good. Accordingly, when the electrolyte liquid leaks from each liquid chamber 53 to each second chamber 55 , the leaked liquid stays at the bottom of the second vessel 72 .
- the gas component inside the second vessel 72 flows from the top of the second vessel 72 to the blower 73 .
- the blower 73 sends out the gas in the carbon dioxide circulation passage 71 toward the third vessel 74 side.
- a carbon dioxide return passage 75 for returning the circulating carbon dioxide gas to the inlet of the cathode chamber 11 of the electrolytic reduction device 2 is connected to the carbon dioxide circulation passage 71 .
- the carbon dioxide return passage 75 is preferably connected to the third vessel 74 and the first supply passage 26 .
- a pressure control valve 76 is provided in the carbon dioxide return passage 75 .
- Each inlet of each liquid chamber 53 is connected to an electrolyte tank 82 via an electrolyte supply passage 81 .
- the electrolyte supply passage 81 is branched corresponding to each liquid chamber 53 .
- a pump 83 , a flow control valve (pressure control valve) 84 , and a temperature controller 85 are provided in order from the electrolyte tank 82 side in the electrolyte supply passage 81 .
- the pump 83 pumps the electrolytic solution from the electrolytic solution tank 82 to each liquid chamber 53 .
- a temperature controller 85 adjusts the temperature of the electrolyte.
- the temperature controller 85 adjusts the electrolytic solution from room temperature to 80° C. or less, for example.
- Each outlet of each liquid chamber 53 is connected to the electrolyte tank 82 via a first electrolyte return passage 87 .
- the electrolyte circulates through the electrolyte tank 82 , the electrolyte supply passage 81 , the liquid chambers 53 , and the first electrolyte return passage 87 .
- a portion of the electrolyte supply passage 81 between the pump 83 and the flow control valve 84 is connected to the electrolyte tank 82 via a circulation passage 88 .
- the circulation passage 88 is provided with an electrolytic solution sensor CS1 that detects information including at least one of the composition and concentration of the electrolytic solution passing through the circulation passage 88 .
- the electrolyte sensor CS1 may be, for example, an absorption photometer or a conductivity sensor.
- the absorption photometer may be a UV-visible spectrophotometer.
- the electrolyte tank 82 is connected to the high-concentration electrolyte tank 92 via an electrolyte supply passage 91 .
- a high-concentration electrolytic solution is stored in the high-concentration electrolytic solution tank 92 .
- the high-concentration electrolyte has a higher concentration of the electrolyte and the compound that adsorbs and desorbs protons with oxidation-reduction, which will be described later, than the electrolyte stored in the electrolyte tank 82 .
- Electrolyte replenishment passage 91 is provided with a pump 93 that feeds the high-concentration electrolyte from high-concentration electrolyte tank 92 toward electrolyte tank 82 .
- the bottom of the second vessel 72 is connected to the electrolyte tank 82 via the second electrolyte return passage 95 .
- a pump 96 that delivers the electrolyte from the second vessel 72 toward the electrolyte tank 82 is provided in the second electrolyte return passage 95 .
- the electrolyte separated from the carbon dioxide gas and accumulated in the bottom of the second vessel 72 is returned to the electrolyte tank 82 via the second electrolyte return passage 95 .
- the top of the electrolyte tank 82 is connected to the portion between the pressure control valves 68 and 69 in the second generated gas outlet passage 66 via the gas return passage 97 .
- a temperature controller 98 is provided in the gas return passage 97 .
- the gas-phase pressure of the electrolyte tank 82 is controlled by a pressure control valve 69 , and the gas in the electrolyte tank 82 flows to the second generated gas outlet passage 66 .
- the first vessel 65 and the third vessel 74 are provided with pressure sensors PS1 and PS2 for measuring the internal pressure of the respective gas phase portions.
- a pressure sensor PS3 for measuring the internal pressure is provided in the portion between the flow control valve 84 and the end portion of the liquid chamber 53 side of the electrolytic solution supply passage 81 .
- the electrolyte tank 82 is provided with a pressure sensor PS4 for measuring the internal pressure of the gas phase portion.
- a flow rate sensor FS1 is provided in a portion of the mixed gas inlet passage 62 closer to the first chamber 54 than the blower 63 is.
- a flow rate sensor FS2 is provided in a portion of the carbon dioxide circulation passage 71 between the blower 73 and the third vessel 74 .
- a flow sensor FS3 is provided in a portion of the electrolytic solution supply passage 81 between the pump 83 and the flow control valve 84 .
- the electrolyte tank 82 is provided with a temperature sensor TS1 that measures the temperature of the charge liquid inside.
- Each pressure sensor PS1-PS4, each flow rate sensor FS1-FS3, and temperature sensor TS1 are connected to the control device .
- the pressure sensor PS1 may be provided in a portion of the mixed gas inlet passage 62 between the blower 63 and the first chamber 54 .
- the pressure sensor PS3 may be provided in the first electrolytic solution return passage 87 .
- the electrolyte is composed of a solute and a solvent in which the solute is dissolved.
- a solute produces carbonic acid when dissolved in a solvent, or produces hydrogen carbonate ions and carbonate ions by ionization.
- the solute may include, for example, at least one selected from the group consisting of alkali metal hydrogen carbonates, carbonates, alkaline earth metal hydrogen carbonates, and carbonates.
- the solute may specifically be NaHCO 3 , KHCO 3 , LiHCO 3 , Na 2 CO 3 , K 2 CO 3 , Li 2 CO 3 .
- the solvent may be water.
- a compound that adsorbs and desorbs protons during oxidation-reduction is dissolved in the electrolytic solution.
- the compound is preferably an organic compound having an oxidation-reduction potential of -1.0 V to 1.0 V based on the standard hydrogen electrode potential at pH 7.
- the compound is, for example, a quinone-based compound, an indophenol-based compound, an indigo-based compound, etc., and a quinone-based compound is preferable.
- the quinone-based compound includes a hydroquinone-based compound containing a hydroxy group, and a benzoquinone-based compound obtained by oxidation of a hydroquinone-based compound and containing a carbonyl group.
- the quinone-based compound contained in the electrolyte has a functional group with a relatively high electron-withdrawing property compared to oxygen.
- the quinone compound is more easily reduced than oxygen, and the benzoquinone compound containing a carbonyl group is reduced to the hydroquinone compound containing a hydroxy group, whereas oxygen is less likely to be reduced.
- the functional group of the quinone compound may be sulfonate.
- the sulfonate has a sulfo group (--SO 3 ) and an alkali metal element, and may be, for example, sodium sulfonate or potassium sulfonate.
- a sulfo group (--SO 3 ) and an alkali metal element
- the number of functional groups should be one or more, and from the viewpoint of enhancing the electron-withdrawing property, the number is preferably two or more and four or less.
- a quinone-based compound is a hydroquinone-based compound that contains a hydroxy group in addition to the above functional groups after a reduction reaction. From the viewpoint of ensuring aromaticity, the number of hydroxy groups is preferably 2 or more and 4 or less.
- the hydroquinone compound may be, for example, disodium 4,5-dihydroxy-1,3-benzenedisulfonate (Tiron) or potassium hydroquinonesulfonate.
- a quinone-based compound is a benzoquinone-based compound that contains a carbonyl group in addition to the above functional groups after an oxidation reaction.
- the benzoquinone-based compound becomes a compound in which a hydroxy group is substituted with a carbonyl group by an oxidation reaction at the second gas diffusion electrode 52 .
- the chemical formula (6) of the benzoquinone compound is shown below.
- R 1 to R 4 are H (hydrogen), functional groups, or the like.
- the chemical formula (7) of 4,5-dihydroxy-1,3-benzenedisulfonic acid is shown.
- the pH on the first gas diffusion electrode 51 side becomes relatively high, and the pH on the second gas diffusion electrode 52 side becomes relatively low. Thereby, a pH gradient is formed in the electrolytic solution, and hydrogen carbonate ions, carbonic acid, and carbonate ions can be moved to the second gas diffusion electrode 52 side. Thereby, the gas flow rate of carbon dioxide that can be separated into the second chamber 55 can be increased.
- the mixed gas (produced gas) from which carbon dioxide has been separated flows from each first chamber 54 through the first vessel 65 to the second produced gas outlet passage 66 .
- the carbon dioxide gas separated into the second chambers 55 circulates through the carbon dioxide circulation passage 71 and each of the second chambers 55 .
- the electrolyte is separated from the carbon dioxide gas in the second vessel 72 and returned to the electrolyte tank 82 via the second electrolyte return passage 95 .
- the carbon dioxide gas flowing through the carbon dioxide circulation passage 71 is returned to the electrolytic reduction device 2 through the carbon dioxide return passage 75 and the first supply passage 26 by opening the pressure control valve 76 .
- the electrolytic reduction device 2 uses carbon dioxide separated from the generated gas in the carbon dioxide separation device 3 as part of the raw material.
- the controller 7 controls the pressure PL1 of the first chamber 54, the pressure PL2 of the second chamber 55, the pressure PL3 of the liquid chamber 53, and the electrolyte tank 82 based on the signals from the pressure sensors PS1, PS2, PS3, and PS4. Pressure PL4 is detected.
- the control device 7 controls the pressure of the first vessel 65 detected by the pressure sensor PS1 as the pressure PL1 of the first chamber 54, the pressure of the third vessel 74 detected by the pressure sensor PS2 as the pressure PL2 of the second chamber 55, and the pressure sensor PS3. is preferably set to the pressure PL3 of the liquid chamber 53 in the electrolyte supply passage 81 detected by .
- the control device 7 performs pressure control so that the pressure PL1 of each first chamber 54 is equal to or higher than the pressure PL3 of each liquid chamber 53, and the pressure PL3 of each liquid chamber 53 is equal to or higher than the pressure PL2 of each second chamber 55.
- Control valves 68, 76 and flow control valve 84 (PL1 ⁇ PL3 ⁇ PL2).
- control device 7 controls the pressure PL1 of each first chamber 54 to be equal to or higher than the pressure PL3 of each liquid chamber 53, the pressure PL3 of each liquid chamber 53 to be equal to or higher than the pressure PL4 of the electrolyte tank 82, and
- the pressure control valves 68, 69, 76 and the flow control valve 84 are preferably controlled so that the pressure PL4 of the tank 82 becomes equal to or higher than the pressure PL2 of each second chamber 55 (PL1 ⁇ PL3 ⁇ PL4 ⁇ PL2).
- each liquid chamber 53 becomes equal to or higher than the pressure PL4 of the electrolyte tank 82, even if gas enters the liquid chamber 53 from the first chamber 54, the gas and the electrolyte in the electrolyte tank 82 do not mix. Separation is encouraged.
- the pressure PL3 of each liquid chamber 53 becomes equal to or higher than the pressure PL2 of each second chamber 55, carbon dioxide in the electrolytic solution can easily pass through the second gas diffusion electrode 52 and be released into the second chamber 55. .
- the electrolyte leaked into each second chamber 55 is separated by the second vessel 72 and returned to the electrolyte tank 82 .
- the control device 7 acquires the concentration of the quinone compound in the electrolyte based on the signal from the electrolyte sensor CS1, and drives the pump 93 to increase the concentration when the concentration of the quinone compound is equal to or lower than a predetermined judgment value.
- a high concentration electrolyte is supplied from the concentration electrolyte tank 92 to the electrolyte tank 82 .
- the high-concentration electrolyte has a higher concentration of the quinone-based compound and the electrolyte than the electrolyte supplied to each liquid chamber 53 . As a result, the concentration of the quinone-based compound in the electrolytic solution increases, and the concentration of the quinone-based compound in the charge liquid is maintained within a predetermined range.
- the generated gas from which carbon dioxide has been separated in the carbon dioxide separator 3 passes from the second generated gas outlet passage 66 to the moisture remover 4 via the passage 101.
- the passage 101 is provided with a compressor 102 for pumping the first processing gas toward the water removing device 4 .
- the moisture remover 4 separates water from the first treated gas.
- the water removing device 4 has a first water removing device 4A and a second water removing device 4B provided in parallel.
- the first and second moisture removal devices 4A, 4B may be adsorption towers filled with a moisture adsorbent.
- the moisture adsorbent releases (desorbs) moisture by being subjected to heat treatment.
- the moisture adsorbent is preferably a desiccant such as crystalline zeolite (molecular sieve).
- the inlet of the first moisture removing device 4A is connected to the passage 101 via the passage 103.
- a passage 104 is connected to the outlet of the first water removing device 4A.
- the inlet of the second moisture removing device 4B is connected to the passage 101 via the passage 105.
- a passage 106 is connected to the outlet of the second water removing device 4B.
- Passage 104 and passage 106 are connected to the inlet of product gas separation device 5 via passage 107 .
- On/off valves 111-114 are provided in passages 103-106, respectively.
- the first and second moisture removing devices 4A, 4B are connected to the purge gas circulation passage 116.
- the purge gas circulation passage 116 extends from a passage 121 extending from a portion of the passage 103 between the on/off valve 111 and the first moisture removing device 4A, and from a portion of the passage 105 between the on/off valve 113 and the second moisture removing device 4B.
- On/off valves 126, 127, 128 and 129 are provided in passages 121, 122, 124 and 125, respectively.
- the circulation passage 123 is provided with a first heat exchanger 131, a cooler 132, a gas-liquid separator 133, a blower 134, a flow control valve 135, a first heat exchanger 131, and a combustion furnace 6 in this order from the passage 121 side. ing.
- a portion of circulation passage 123 between flow control valve 135 and first heat exchanger 131 is connected to passage 107 via passage 138 .
- a flow control valve 139 is provided in the passage 107 .
- a portion of the circulation passage 123 between the blower 134 and the flow control valve 135 is connected to the passage 101 via a return passage 141 .
- the combustion chamber of the combustion furnace 6 is connected to the anode outlet passage 42 of the electrolytic reduction device 2 through a passage 142.
- a second heat exchanger 143 is provided in the passage 142 .
- a passage 144 through which hydrogen and carbon monoxide separated in the produced gas separation device 5 flow is connected to a portion of the passage 142 between the electrolytic reduction device 2 and the second heat exchanger 143 .
- An oxygen supply source 147 is connected through a flow control valve 146 to a portion of the passage 142 between the electrolytic reduction device 2 and the second heat exchanger 143 .
- a fuel supply source 149 is connected to the passage 144 via a flow control valve 148 .
- Fuel supply 149 may be a tank or pipeline that supplies a gaseous fuel such as natural gas or hydrogen. Gaseous fuel supplied from fuel supply 149 mixes with hydrogen and carbon monoxide flowing through passage 144 . Oxygen and fuel containing hydrogen and carbon monoxide are mixed in passage 142 and supplied to combustion furnace 6 after being heated in second heat
- the combustion furnace 6 is preferably an oxygen combustion furnace.
- the oxygen supplied from the passage 142 and the fuel containing hydrogen and carbon monoxide are combusted.
- Exhaust gas generated by combustion mainly contains carbon dioxide and water.
- Exhaust gas is supplied from the combustion furnace 6 to the first supply passage 26 through the exhaust gas passage 151 .
- the exhaust gas passage 151 may be provided with a blower 150 that sends the exhaust gas to the first supply passage 26 .
- carbon dioxide contained in the exhaust gas is reused as part of the raw material in the electrolytic reduction device 2 .
- the exhaust gas passage 151 passes through the second heat exchanger 143 .
- the exhaust gas and the gas containing fuel and oxygen flowing through the passage 142 exchange heat in the second heat exchanger 143, and the temperature of the gas flowing through the passage 142 rises.
- the first and second moisture removal devices 4A and 4B perform an adsorption step of adsorbing water from the generated gas and a desorption step of receiving heat generated in the combustion furnace 6 and releasing the water adsorbed in the adsorption step. . While one of the first and second moisture removal devices 4A, 4B is performing the adsorption step, the other of the first and second moisture removal devices 4A, 4B is performing the desorption step.
- the first and second moisture removal devices 4A and 4B are preferably switched between the adsorption process and the desorption process at predetermined time intervals.
- the first moisture removal device 4A performs the adsorption process and the second moisture removal device 4B performs the desorption process. Execute the separate process.
- the first process gas flowing through the passage 101 passes through the first moisture removing device 4A and is dehydrated.
- the first processed gas from which water has been removed by the first water remover 4A or the second water remover 4B is referred to as a second processed gas.
- Most of the second process gas is sent to product gas separator 5 via passage 107 .
- part of the second process gas passes through the passage 138 and is supplied to the circulation passage 123 by opening the flow control valve 139 .
- Part of the second processing gas circulates through the purge gas circulation passage 116 as purge gas.
- the purge gas flowing through the circulation passage 123 is heated in the combustion furnace 6. At this time, the purge gas exchanges heat with the fuel, oxygen, and exhaust gas without being mixed.
- the purge gas heated in the combustion furnace 6 is supplied through the passage 125 to the second moisture removing device 4B. As a result, the moisture adsorbent of the second moisture remover 4B is heated by the purge gas, and moisture is desorbed from the moisture adsorbent. Thereby, the moisture adsorbent of the second moisture removing device 4B is regenerated.
- the moisture desorbed from the moisture adsorbent passes through the first heat exchanger 131 and cooler 132 together with the purge gas and is cooled.
- the moisture-containing purge gas is cooled by exchanging heat with the purge gas that has passed through the flow control valve 135 in the first heat exchanger 131 .
- the purge gas containing moisture is further cooled in the cooler 132 to liquefy the moisture.
- the moisture-containing purge gas that has passed through the cooler 132 is separated from liquid water in the gas-liquid separator 133 .
- the liquid water separated by the gas-liquid separator 133 is supplied to the second supply passage 33 through the passage 152 and sent to the anode chamber 12 of the electrolytic reduction device 2 .
- the second moisture removal device 4B By opening the on/off valves 113, 114, 126 and 128 and closing the on/off valves 111, 112, 127 and 129, the second moisture removal device 4B performs the adsorption process and the first moisture removal device 4A performs the desorption process. Execute the separate process. As a result, the first process gas flowing through the passage 101 is dehydrated in the second moisture removal device 4B and then sent to the generated gas separation device 5 . Also, the heated purge gas is supplied to the first moisture removing device 4A to regenerate the moisture adsorbent of the first moisture removing device 4A.
- the product gas separation device 5 separates hydrocarbons from the second treated gas.
- the product gas separator 5 may be a cryogenic separator.
- the product gas separation device 5 separates methane and ethylene from the second treated gas independently of each other.
- the off-gas from which methane and ethylene are separated from the second treated gas mainly contains carbon monoxide and hydrogen.
- the off-gas is sent to combustion furnace 6 via passage 144 and passage 142 and used as fuel. Incidentally, when carbon monoxide is the target substance, it is also possible to recover hydrogen and carbon monoxide.
- a flow rate sensor FS4 for measuring the flow rate of the gas supplied to the cathode chamber 11 of the electrolytic reduction device 2 is provided at the end of the first supply passage 26 on the electrolytic reduction device 2 side.
- the cathode outlet passage 39 is provided with a flow rate sensor FS5 for measuring the flow rate of the generated gas passing therethrough and a gas composition sensor CS2 for detecting the composition of the generated gas.
- the carbon dioxide return passage 75 is provided with a flow rate sensor FS6 that measures the flow rate of carbon dioxide gas passing therethrough.
- a flow rate sensor FS7 for measuring the flow rate of the second processing gas passing through the passage 138 is provided in the portion between the flow control valve 139 and the passage 107 of the passage 138 .
- a flow rate sensor FS8 is provided between the blower 134 and the flow rate control valve 135 of the circulation passage 123 to measure the flow rate of the purge gas passing therethrough.
- a flow rate sensor FS9 for measuring the flow rate of the off-gas passing through the passage 144 is provided in the portion between the fuel supply source 149 and the product gas separation device 5 .
- a temperature sensor TS2 for measuring the temperature of the purge gas passing through the circulation passage 123 between the combustion furnace 6 and the passages 124 and 125 is provided.
- An oxygen concentration sensor OS1 for measuring the oxygen concentration in the gas containing fuel and oxygen supplied to the combustion furnace 6 is provided at the end of the passage 142 on the second heat exchanger 143 side.
- the control device 7 acquires the flow rate and composition of the generated gas flowing through the cathode outlet passage 39 based on the signals from the flow rate sensor FS5 and the gas composition sensor CS2, and the DC power supply 19 supplies based on the flow rate and composition of the generated gas. Current should be controlled.
- the controller 7 preferably increases the current supplied by the DC power supply 19 as the flow rate of the produced gas decreases or as the concentration of ethylene decreases.
- the control device 7 acquires the flow rate of carbon dioxide flowing through the carbon dioxide return passage 75 based on the signal from the flow rate sensor FS6, and adjusts the opening degree of the flow control valve 29 based on the flow rate of carbon dioxide flowing through the carbon dioxide return passage 75. should be controlled.
- the controller 7 preferably increases the opening degree of the flow control valve 29 as the flow rate of carbon dioxide flowing through the carbon dioxide return passage 75 decreases.
- the control device 7 preferably acquires the flow rate of the purge gas flowing through the circulation passage 123 based on the signal from the flow sensor FS8, and controls the opening degree of the flow control valve 139 based on the flow rate of the purge gas flowing through the circulation passage 123.
- the controller 7 preferably increases the opening degree of the flow control valve 139 as the flow rate of the purge gas flowing through the circulation passage 123 decreases.
- the control device 7 acquires the temperature of the purge gas supplied to the first or second moisture removing device 4A, 4B based on the signal from the temperature sensor TS2, and opens the flow control valves 146, 148 based on the temperature of the purge gas. It is good to control the degree.
- the controller 7 preferably increases the opening degrees of the flow control valves 146 and 148 when the temperature of the purge gas is equal to or lower than the predetermined lower limit.
- the control device 7 preferably acquires the oxygen concentration of the gas flowing through the passage 142 based on the signal from the oxygen concentration sensor OS1, and controls the opening degree of the flow control valve 146 based on the oxygen concentration.
- the controller 7 preferably increases the opening of the flow control valve 146 when the oxygen concentration of the gas flowing through the passage 142 is equal to or lower than a predetermined lower limit.
- the control device 7 preferably acquires the flow rate of the off-gas flowing through the passage 144 based on the signal from the flow sensor FS9, and controls the opening degree of the flow control valve 148 based on the flow rate of the off-gas.
- the control device 7 preferably increases the degree of opening of the flow control valve 148 as the flow rate of the off-gas decreases.
- the effect of the carbon dioxide recovery system 1 will be described below. Since the carbon dioxide in the generated gas discharged from the electrolytic reduction device 2 is separated from the generated gas in a gaseous state by the carbon dioxide separation device 3, the carbon dioxide can be easily recovered and reused.
- the carbon dioxide separator 3 using electrochemistry can separate carbon dioxide from hydrocarbons with less energy than the separation method using amine. Thereby, in the carbon dioxide recovery system 1, energy efficiency can be improved.
- the moisture adsorbent of the moisture remover 4 is regenerated using the combustion heat of the oxygen generated at the anode 17 of the electrolytic reduction apparatus 2 and the off-gas containing carbon monoxide and hydrogen separated from the produced gas. Thereby, the energy efficiency of the carbon dioxide recovery system 1 can be improved. In addition, since the carbon dioxide and water generated by the combustion of the off-gas are reused as raw materials for the electrolytic reduction device 2, the amount of carbon dioxide emitted to the external environment can be reduced.
- the water removing device 4 has first and second water removing devices 4A and 4B provided in parallel. Therefore, one of the first and second moisture removal devices 4A, 4B can perform the adsorption step and the other can perform the desorption step. This enables continuous operation of the electrolytic reduction device 2 .
- the carbon dioxide separator 3 includes a first unit in which a first gas diffusion electrode 51, a liquid chamber 53, and a second gas diffusion electrode 52 are arranged in this order; It has a stack 59 in which a plurality of second units arranged in order of the electrodes 51 are alternately arranged at intervals. Thereby, the carbon dioxide separator 3 can be formed compactly.
- Each liquid chamber 53 is connected to an electrolytic solution tank 82 to circulate the electrolytic solution. Therefore, the electrolyte can be easily replenished and replaced, and the quality of the electrolyte can be maintained. This keeps the carbon dioxide separation capacity constant.
- the carbon dioxide recovery system 200 according to the second embodiment differs from the carbon dioxide recovery system 1 according to the first embodiment in that a passage 142 has a carbon dioxide separator 201 .
- Other configurations of the carbon dioxide recovery system 200 according to the second embodiment are the same as those of the carbon dioxide recovery system 1 according to the first embodiment.
- the carbon dioxide separator 201 has the same configuration as the carbon dioxide separator 3 shown in FIG.
- the carbon dioxide separation device 201 separates carbon dioxide from the gas discharged from the anode outlet passage 42 of the electrolytic reduction device 2 .
- the gas discharged from the anode outlet passage 42 of the electrolytic reduction device 2 contains oxygen as a main component and may contain a very small amount of carbon dioxide.
- the gas discharged from the anode outlet passage 42 of the electrolytic reduction device 2 is supplied to each first chamber 54 through the mixed gas inlet passage 62 of the carbon dioxide separation device 201, and carbon dioxide is separated.
- a gas discharged from each first chamber 54 of the carbon dioxide separator 201 is called a third processed gas.
- the main component of the third process gas is oxygen.
- the third process gas is supplied to combustion furnace 6 through passage 142 through second heat exchanger 143 .
- the carbon dioxide return passage 75 of the carbon dioxide separator 201 is connected to the first supply passage 26 by the carbon dioxide return passage 202 .
- the carbon dioxide separated from the gas discharged from the anode outlet passage 42 of the electrolytic reduction device 2 is returned to the electrolytic reduction device 2 via the carbon dioxide return passage 202 and the first supply passage 26, and is one of the raw materials. used as a part.
- a flow rate sensor FS10 for measuring the flow rate of the gas flowing inside and a gas composition sensor CS3 for detecting the composition of the gas flowing inside.
- the carbon dioxide return passage 202 is provided with a flow rate sensor FS11 for measuring the flow rate of carbon dioxide gas flowing therein.
- the control device 7 acquires the flow rate and composition of the gas flowing through the passage 142 based on the signals from the flow rate sensor FS10 and the gas composition sensor CS3, and controls the current supplied by the DC power supply 19 based on the flow rate and composition of the gas. good.
- the control device 7 preferably increases the current supplied by the DC power supply 19 as the gas flow rate decreases or as the oxygen concentration decreases.
- the control device 7 acquires the flow rate of carbon dioxide flowing through the carbon dioxide return passage 202 based on the signal from the flow sensor FS11, and adjusts the opening degree of the flow control valve 29 based on the flow rate of carbon dioxide flowing through the carbon dioxide return passage 202. should be controlled.
- the controller 7 preferably increases the opening degree of the flow control valve 29 as the flow rate of carbon dioxide flowing through the carbon dioxide return passage 202 decreases.
- the carbon dioxide recovery system 200 even if carbon dioxide leaks from the cathode chamber 11 to the anode chamber 12 through the membrane electrode assembly 10 of the electrolytic reduction device 2, the leaked carbon dioxide is It can be recovered in the carbon dioxide separation device 201 and reused as a raw material for the electrolytic reduction device 2 .
- the carbon dioxide separation device 3 of the first and second embodiments is replaced with a carbon dioxide separation device 300 .
- the carbon dioxide separation device 300 has a partially changed configuration compared to the carbon dioxide separation device 3 .
- the same components as those of the carbon dioxide separator 3 are denoted by the same reference numerals, and description thereof is omitted.
- each first chamber 54 is arranged above the outlet.
- the first vessel 65 functions as a gas-liquid separator.
- the bottom of the first vessel 65 is positioned below each outlet of each first chamber 54 and each first product gas outlet passage 64 descends from each outlet of each first chamber 54 toward the first vessel 65 . I hope you are. Accordingly, when the electrolyte liquid leaks from each liquid chamber 53 to each first chamber 54 , the leaked liquid stays at the bottom of the first vessel 65 .
- the gas component in the first vessel 65 flows from the top of the first vessel 65 to the second generated gas outlet passage 66 .
- the bottom of the first vessel 65 is connected to the electrolyte tank 82 via the second electrolyte return passage 95 .
- a pump 96 that delivers the electrolyte from the first vessel 65 toward the electrolyte tank 82 is provided in the second electrolyte return passage 95 .
- the electrolyte separated from the generated gas and accumulated at the bottom of the first vessel 65 is returned to the electrolyte tank 82 via the second electrolyte return passage 95 .
- the control device 7 performs pressure control so that the pressure PL2 of each second chamber 55 is equal to or higher than the pressure PL3 of each liquid chamber 53, and the pressure PL3 of each liquid chamber 53 is equal to or higher than the pressure PL1 of each first chamber 54.
- Control valves 68, V5, V6 (PL2 ⁇ PL3 ⁇ PL1).
- control device 7 controls the pressure PL2 of each second chamber 55 to be equal to or higher than the pressure PL3 of each liquid chamber 53, the pressure PL3 of each liquid chamber 53 to be equal to or higher than the pressure PL4 of the electrolyte tank 82, and
- the pressure control valves 68, 69, 76 and the flow control valve 84 may be controlled so that the pressure PL4 of the tank 82 becomes equal to or higher than the pressure PL1 of each first chamber 54 (PL2 ⁇ PL3 ⁇ PL4 ⁇ PL1).
- the carbon dioxide separation device 3 of the first and second embodiments is replaced with a carbon dioxide separation device 400 .
- the carbon dioxide separation device 400 includes a carbon dioxide gas absorption part 401, an electrochemical cell 402, a first passage 403, a second passage 404, a third passage 405, and a gas-liquid separator. 406.
- the carbon dioxide gas absorption part 401 brings an electrolytic solution containing a compound that adsorbs and desorbs protons with oxidation-reduction into contact with the mixed gas, and causes the electrolytic solution to absorb carbon dioxide in the mixed gas.
- the electrolytic solution may be the same as the electrolytic solution flowing through the carbon dioxide separator 3 of the first embodiment.
- the electrolytic solution may be, for example, potassium hydroquinone sulfonate.
- the carbon dioxide gas absorption part 401 may bring the mixed gas and the electrolytic solution into contact by, for example, countercurrent contact, parallel current contact, or bubbling.
- the carbon dioxide gas absorption part 401 may spray the electrolytic solution toward the mixed gas, or may use a hollow fiber membrane to bring the mixed gas and the electrolytic solution into contact with each other.
- the carbon dioxide gas absorption part 401 includes a gas inlet 411 to which the mixed gas is supplied, a gas outlet 412 to discharge the mixed gas, an electrolytic solution inlet 413 to which the electrolytic solution is supplied, and an electrolytic solution outlet 414 to discharge the electrolytic solution.
- the electrochemical cell 402 is partitioned into a cathode chamber 417 and an anode chamber 418 by a membrane electrode assembly 416 .
- Membrane electrode assembly 416 includes electrolyte membrane 416 A, cathode 416 B and anode 416 C provided on both sides of electrolyte membrane 416 A and connected to power supply 419 .
- Cathode 416 B is located in cathode chamber 417 and anode 416 C is located in anode chamber 418 .
- Cathode 416B is connected to the negative pole of power supply 419 and anode 416C is connected to the positive pole of power supply 419 .
- the electrolyte membrane 416A, cathode 416B, and anode 416C may have the same configurations as the electrolyte membrane 15, cathode 16, and anode 17 of the first embodiment. Also, the cathode 416B and the anode 416C may have the same configurations as the first gas diffusion electrode 51 and the second gas diffusion electrode 52 of the first embodiment.
- the first passage 403 connects the electrolyte outlet 414 of the carbon dioxide gas absorption part 401 and the anode chamber 418 of the electrochemical cell 402 .
- the first passage 403 allows the electrolytic solution to flow from the carbon dioxide gas absorbing portion 401 to the anode chamber 418 .
- a pump for transporting the electrolytic solution may be provided in the first passage 403 .
- the second passage 404 connects the anode chamber 418 and the cathode chamber 417 and allows the electrolytic solution to flow from the anode chamber 418 to the cathode chamber 417 .
- a gas-liquid separator 406 is provided in the second passage 404 . The gas-liquid separator 406 separates the electrolyte and the gas component in the electrolyte.
- the third passage 405 connects the cathode chamber 417 of the electrochemical cell 402 and the electrolyte inlet 413 of the carbon dioxide gas absorption part 401 .
- the third passage 405 allows the electrolytic solution to flow from the cathode chamber 417 to the carbon dioxide gas absorbing portion 401 .
- the third passage 405 may be provided with a pump for transporting the electrolytic solution.
- the electrolytic solution circulates through the carbon dioxide gas absorber 401, the first passage 403, the anode chamber 418, the second passage 404, the gas-liquid separator 406, the cathode chamber 417, and the third passage 405 in this order. do.
- the electrolyte is reduced in the cathode chamber 417 and the pH increases.
- the carbon dioxide gas in the mixed gas is dissolved in the electrolytic solution due to the contact between the electrolytic solution having a relatively high pH and the mixed gas.
- the chemical reactions at this time are similar to those of chemical formulas (9) to (11) above.
- Carbon dioxide takes the form of bicarbonate ions in the electrolyte. This removes carbon dioxide gas from the mixed gas.
- the mixed gas from which the carbon dioxide gas has been removed is discharged from the gas outlet 412 and sent to the water removing device 4 through the passage 101 .
- the electrolytic solution in which carbon dioxide is dissolved is sent to the anode chamber 418 via the first passage 403 .
- the electrolyte is oxidized and the pH of the electrolyte is lowered.
- the pH of the electrolyte flowing from the anode chamber 418 to the second passage 404 will be lower than the pH of the electrolyte flowing from the cathode chamber 417 to the third passage 405 .
- hydrogen carbonate ions in the electrolyte receive protons and change to carbon dioxide.
- the chemical reactions at this time are similar to those of chemical formulas (9) to (11) above. As a result, carbon dioxide becomes gas and desorbs from the electrolytic solution.
- the carbon dioxide gas and the electrolyte separated from the electrolyte in the anode chamber 418 are sent to the gas-liquid separator 406 via the second passage 404 .
- the gas-liquid separator 406 separates the carbon dioxide gas and the electrolytic solution.
- the electrolyte flows from the gas-liquid separator 406 to the cathode chamber 417 via the second passage 404 .
- Carbon dioxide gas flows from the gas-liquid separator 406 to the electrolytic reduction device 2 through the carbon dioxide return passage 75 .
- the electrolytic solution is reduced and its pH rises, and becomes ready to absorb carbon dioxide gas again.
- the potential difference between the cathode 416B and the anode 416C can be reduced, and the energy efficiency can be improved.
- FIG. 8 shows a more detailed configuration of the carbon dioxide separator 400 described above.
- the carbon dioxide gas absorbing part 401 has a vertically extending housing 431 .
- An electrolytic solution is stored in the bottom of the housing 431 .
- a gas inlet 411 through which mixed gas is supplied is provided at the bottom of the housing 431 .
- a gas outlet 412 through which mixed gas is discharged is provided at the upper end of the housing 431 .
- the carbon dioxide gas absorbing part 401 is provided in the upper part of the housing 431, and includes a nozzle 432 for injecting the electrolytic solution, a fourth passage 433 for supplying the electrolytic solution stored in the bottom part of the housing 431 to the nozzle 432, and the housing.
- a tray 434 is provided between the gas inlet 411 and the nozzle 432 at 431 and temporarily stores the electrolytic solution injected from the nozzle 432 .
- a plurality of trays 434 may be provided.
- Electrolyte outlet 414 may be provided in tray 434 .
- the third passage 405 is connected to the fourth passage 433.
- a connecting portion of the fourth passage 433 with the third passage 405 serves as the electrolyte inlet 413 .
- the third passage 405 is provided with a first flow control valve 436A.
- a second flow control valve 436B is provided in the fourth passage 433 on the bottom side of the housing 431 relative to the third passage 405 .
- a first pump 438A is provided between the third passage 405 and the nozzle 432 in the fourth passage 433 .
- the electrolyte stored in the bottom of the housing 431 is supplied to the nozzle 432 via the fourth passage 433 by the first pump 438A, and the electrolyte is injected from the nozzle 432. As shown in FIG.
- the electrolyte injected from the nozzle 432 flows down inside the housing 431 , passes through the tray 434 and is stored in the bottom of the housing 431 .
- a water supply valve 439 for supplying water may be provided at the bottom of the housing 431 . Water is supplied to the bottom of housing 431 through water valve 439 to dilute the electrolyte.
- a mist eliminator 441 is provided at the gas outlet 412 . The mist eliminator 441 collects electrolyte solution mist floating in the discharged mixed gas.
- the electrochemical cell 402 is partitioned into a plurality of cathode chambers 417 and a plurality of anode chambers 418 by a plurality of membrane electrode assemblies 416 .
- a plurality of membrane electrode assemblies 416 are arranged in parallel with each other at intervals. Adjacent membrane electrode assemblies 416 have their respective cathodes 416B or respective anodes 416C facing each other.
- a plurality of anode chambers 418 and a plurality of cathode chambers 417 are alternately arranged in the electrochemical cell 402 .
- the end of the first passage 403 on the anode chamber 418 side is branched and connected to each of the plurality of anode chambers 418 .
- the end of the second passage 404 on the anode chamber 418 side is branched and connected to each of the plurality of anode chambers 418 .
- the end of the second passage 404 on the cathode chamber 417 side is branched and connected to each of the plurality of cathode chambers 417 .
- the end of the third passage 405 on the cathode chamber 417 side is branched and connected to each of the plurality of cathode chambers 417 .
- a first tank 405A and a second pump 438B are provided in the third passage 405 in order from the electrochemical cell 402 side.
- a first flow control valve 436 A is provided between the second pump 438 B and the electrolyte inlet 413 .
- the first tank 405A temporarily stores the electrolyte discharged from each cathode chamber 417 .
- the first passage 403 is provided with a second tank 403A, a third pump 438C, and a third flow control valve 436C in this order from the electrolyte outlet 414 side.
- the second tank 403A temporarily stores the electrolyte discharged from the electrolyte outlet 414 . Also, the electrolyte collected in the mist eliminator 441 flows into the second tank 403A.
- the second passage 404 is provided with a gas-liquid separator 406, a fourth pump 438D, and a fourth flow control valve 436D in this order from the anode chamber 418 side.
- a gas outlet 412 of the gas-liquid separator 406 is connected to the carbon dioxide return passage 75 via a fifth flow control valve 436E.
- a flow meter FS21 for measuring the flow rate of the electrolytic solution flowing therein is provided in the portion between the first flow control valve 436A and the fourth passage 433 in the third passage 405.
- a flow meter FS22 is provided between the first pump 438A and the nozzle 432 in the fourth passage 433 to measure the flow rate of the electrolytic solution flowing therein.
- a portion of the first passage 403 between the third flow control valve 436C and the anode chamber 418 is provided with a flow meter FS23 for measuring the flow rate of the electrolyte flowing therein.
- a flow meter FS24 is provided between the fourth flow control valve 436D and the cathode chamber 417 in the second passage 404 to measure the flow rate of the electrolyte flowing therein.
- the housing 431 is provided with a pH sensor pHS1 that measures the pH of the electrolyte stored in the bottom of the housing 431 .
- a pH sensor pHS2 for measuring the pH of the electrolyte flowing therein is provided in the portion of the fourth passage 433 between the first pump 438A and the nozzle 432 .
- the third passage 405 is provided with a pH sensor pHS3 that measures the pH of the electrolyte flowing through the third passage 405 .
- the pH sensor pHS3 may be provided, for example, in the first tank 405A.
- the first passage 403 is provided with a pH sensor pHS4 that measures the pH of the electrolyte flowing through the first passage 403 .
- the pH sensor pHS4 may be provided, for example, in the second tank 403A.
- the housing 431 is provided with a liquid level gauge LS1 that measures the liquid level of the electrolyte stored at the bottom thereof.
- the first tank 405A is provided with a liquid level gauge LS2 for measuring the liquid level of the electrolyte stored therein.
- the second tank 403A is provided with a liquid level gauge LS3 for measuring the liquid level of the electrolyte stored therein.
- the gas-liquid separation device 406 is provided with a liquid level gauge LS4 for measuring the liquid level of the electrolyte stored therein. Further, the gas-liquid separation device 406 is provided with a pressure sensor PS11 for measuring the pressure of the gas phase portion therein.
- the control device 7 includes a power supply 419, first to fourth pumps 438A to 438D, first to fifth flow control valves 436A to 436E, water supply valves 439, first to fourth flow meters 446A to 446D, first to fourth pH It is connected to sensors 447A-447D, first to fourth level gauges 448A-448D, and pressure sensor PS11.
- the control device 7 controls the power source 419, first to fourth pumps 438A to 438D, and first to fifth flow control valves 436A to 436E.
- the pH of the electrolyte stored in the bottom of the housing 431, that is, the pH detected by the pH sensor pHS1 is defined as pH1.
- the pH of the electrolytic solution flowing through the portion of the fourth passage 433 closer to the nozzle 432 than the third passage 405, that is, the pH detected by the pH sensor pHS2 is pH2.
- the pH of the electrolyte flowing through the third passage 405, ie, the pH detected by the pH sensor pHS3, is pH3.
- the pH of the electrolytic solution flowing through the first passage 403, that is, the pH detected by the pH sensor pHS4 is assumed to be pH4.
- the controller 7 controls the power supply 419, the first flow control valve 436A, and the second flow control valve 436B so as to satisfy pH3 ⁇ pH2 ⁇ pH1 ⁇ pH4 ⁇ 5.5.
- the control device 7 controls the fifth flow control valve 436E based on the pressure of the gas phase portion in the gas-liquid separation device 406 acquired by the pressure sensor PS11.
- the carbon dioxide separator 3 according to the first embodiment was produced as follows, and its effect was confirmed.
- the carbon dioxide separator has a first chamber (cathode chamber), a second chamber (anode chamber), and a liquid chamber which are partitioned by a first gas diffusion electrode (negative electrode) and a second gas diffusion electrode (positive electrode).
- a room-type electrolytic cell was used.
- a liquid chamber is formed between the first gas diffusion electrode and the second gas diffusion electrode.
- the first and second chambers are sized such that gas passing through them respectively effectively contacts the first and second gas diffusion electrodes.
- the liquid chamber is formed thin so that the inter-liquid resistance becomes small.
- the first gas diffusion electrode and the second gas diffusion electrode are formed by applying a solution in which 30% by weight of polytetrafluoroethylene (PTFE) is dispersed on the surface of carbon paper (porosity 70%, thickness 0.4 mm), and applying electricity in a nitrogen atmosphere. It was formed by firing in a furnace at a temperature of 350° C. for 20 minutes.
- PTFE polytetrafluoroethylene
- the electrolyte was adjusted as follows. First, an aqueous solution containing 0.7M disodium 4,5-dihydroxy-1,3-benzenedisulfonate and 1M potassium bicarbonate was prepared. 30 mL of this aqueous solution was added to a one-chamber electrolysis cell using carbon paper for the negative electrode and the positive electrode, and constant current electrolysis was performed while humidified carbon dioxide gas was blown in at a flow rate of 100 mL/min. During this time, the amount of hydrogen contained in the gas discharged from the outlet of the electrolytic cell was monitored by gas chromatography. Electrolysis was terminated when the amount was reached.
- a DC voltage was applied to the first gas diffusion electrode and the second gas diffusion electrode, and 20 mL of the electrolytic solution was circulated in the liquid chamber at 5 mL/min.
- 100 mL of product gas containing humidified 2.01 vol% CO2 , 1.00 vol % C2H4 , 0.10 vol % CH4, 0.10 vol% CO, and N2 as balance gas. /min, and N 2 gas was passed through the second chamber at 100 mL/min.
- the composition of the outlet gas of the second chamber was analyzed by gas chromatography. The results are shown in FIG. From FIG. 9 , about 80% of CO2 was recovered with current efficiency, C2H4 and CH4, and CO were below the detection limit. This result confirmed that CO2 from the product gas in the first chamber moved to the second chamber and was separated from the product gas. It was also confirmed that C 2 H 4 , CH 4 and CO did not move to the second chamber.
- Example 2 The same carbon dioxide separator and electrolytic solution as in Example 1 were used. A DC voltage was applied to the first gas diffusion electrode and the second gas diffusion electrode, and 20 mL of the electrolytic solution was circulated in the liquid chamber at 5 mL/min. A generated gas containing humidified 0.201 vol% CO 2 , 1.00 vol% C 2 H 4 , 0.10 vol% O 2 , and N 2 as a balance gas is passed through the first chamber at 100 mL/min, N 2 gas was passed through the second chamber at 100 mL/min. Then, the composition of the outlet gas of the second chamber was analyzed by gas chromatography. The results are shown in FIG. From FIG.
- Reference Signs List 1 Carbon dioxide recovery system 2: Electrolytic reduction device 3, 400: Carbon dioxide separation device 4: Water removal device 4A: First water removal device 4B: Second water removal device 5: Generated gas separation device 6: Combustion furnace 7: Control device 51 : first gas diffusion electrode 52 : second gas diffusion electrode 53 : liquid chamber 54 : first chamber 55 : second chamber 62 : generated gas inlet passage 64 : first generated gas outlet passage 65 : first vessel 66 : Second generated gas outlet passage 68 : Pressure control valve 69 : Pressure control valve 71 : Carbon dioxide circulation passage 72 : Second vessel (gas-liquid separator) 74 : third vessel 75 : carbon dioxide return passage 76 : pressure control valve 81 : electrolyte supply passage 82 : electrolyte tank 84 : pressure control valve 87 : first electrolyte return passage 95 : second electrolyte return passage 116 : Purge gas circulation passage 133 : Gas-liquid separator 401 : Carbon dioxide gas absorption unit 402 : Electrochemical cell
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Abstract
Description
2CO2+12H++12e-→C2H4+4H2O ...(1)
CO2+8H++8e-→CH4+2H2O ...(2)
CO2+2H++2e-→CO+H2O ...(3)
2H++2e-→H2 ...(4)
電解還元装置2のアノードでは、以下の化学式(5)で表されるように、水が酸化されて酸素が生成される。
2H2O→O2+4H++4e- ...(5)
電解還元装置2は、ガス拡散電極であるカソードによって区画されたカソードガス室及びカソード液室と、セパレータによってカソード液室に対して区画され、アノードが配置されたアノード液室とを有する3室型の電解還元装置や、電解質膜をカソードとアノードとで挟んだ膜電極複合体(MEA)を使用した電解還元装置等であるとよい。
Q+2H++2e-→QH2 ...(8)
CO2+H2O⇔H2CO3 ...(9)
H2CO3⇔H++HCO3 - ...(10)
HCO3 -⇔H++CO3 2- ...(11)
QH2→Q+2H++2e- ...(12)
次に、第2実施形態に係る二酸化炭素回収システム200について説明する。図5に示すように、第2実施形態に係る二酸化炭素回収システム200は、第1実施形態に係る二酸化炭素回収システム1と比較して、通路142に二酸化炭素分離装置201を有する点が異なる。第2実施形態に係る二酸化炭素回収システム200の他の構成は、第1実施形態に係る二酸化炭素回収システム1と同様である。
第3実施形態では、第1実施形態及び第2実施形態の二酸化炭素分離装置3が二酸化炭素分離装置300に置換されている。二酸化炭素分離装置300は、二酸化炭素分離装置3と比較して一部の構成が変更されている。二酸化炭素分離装置300において、二酸化炭素分離装置3と同一の構成については同一の符号を付して説明を省略する。
第4実施形態では、第1実施形態及び第2実施形態の二酸化炭素分離装置3が二酸化炭素分離装置400に置換されている。図7に示すように、二酸化炭素分離装置400は、二酸化炭素ガス吸収部401と、電気化学セル402と、第1通路403と、第2通路404と、第3通路405と、気液分離装置406とを有する。
第1実施形態に係る二酸化炭素分離装置3を以下のように作成し、その効果を確認した。二酸化炭素分離装置は、第1ガス拡散電極(負極)及び第2ガス拡散電極(正極)によって区画された、第1室(カソード室)、第2室(アノード室)、及び液室を有する3室型電解セルとした。液室は第1ガス拡散電極及び第2ガス拡散電極の間に形成されている。第1室及び第2室は、それぞれを通過するガスが第1ガス拡散電極及び第2ガス拡散電極と効率的に接触するように大きさが設定されている。また、液室は、液間抵抗が小さくなるように、薄く形成されている。第1ガス拡散電極及び第2ガス拡散電極は、カーボンペーパー(気孔率70%、厚さ0.4mm)の表面にポリテトラフルオロエチレン(PTFE)が30wt%分散した溶液を塗布し、窒素雰囲気電気炉中で350℃の温度において20分間焼成することによって形成した。
実施例1と同様の二酸化炭素分離装置及び電解液を使用した。第1ガス拡散電極及び第2ガス拡散電極に直流電圧を印加し、液室に電解液20mLを5mL/minで循環させた。第1室には、加湿した0.201vol%CO2、1.00vol%C2H4、0.10vol%O2、及びバランスガスとしてのN2を含む生成ガスを100mL/minで流通させ、第2室にはN2ガスを100mL/minで流通させた。そして、第2室の出口ガスの組成をガスクロマトグラフィによって分析した。その結果を図10に示す。図10から、電流効率で約60%のCO2が回収され、C2H4及びCO2は検出下限下であった。この結果から、第1室の生成ガスからCO2が第2室に移動し、生成ガスから分離されることが確認された。また、C2H4及びCO2は、第2室に移動しないことが確認された。
2 :電解還元装置
3、400 :二酸化炭素分離装置
4 :水分除去装置
4A :第1水分除去装置
4B :第2水分除去装置
5 :生成ガス分離装置
6 :燃焼炉
7 :制御装置
51 :第1ガス拡散電極
52 :第2ガス拡散電極
53 :液室
54 :第1室
55 :第2室
62 :生成ガス入口通路
64 :第1生成ガス出口通路
65 :第1ベッセル
66 :第2生成ガス出口通路
68 :圧力制御弁
69 :圧力制御弁
71 :二酸化炭素循環通路
72 :第2ベッセル(気液分離装置)
74 :第3ベッセル
75 :二酸化炭素戻し通路
76 :圧力制御弁
81 :電解液供給通路
82 :電解液タンク
84 :圧力制御弁
87 :第1電解液戻し通路
95 :第2電解液戻し通路
116 :パージガス循環通路
133 :気液分離装置
401 :二酸化炭素ガス吸収部
402 :電気化学セル
403 :第1通路
404 :第2通路
405 :第3通路
406 :気液分離装置
411 :ガス入口
412 :ガス出口
413 :電解液入口
414 :電解液出口
416 :膜電極複合体
416A :電解質膜
416B :カソード
416C :アノード
417 :カソード室
418 :アノード室
419 :電源
431 :ハウジング
432 :ノズル
433 :第4通路
434 :トレイ
436A :第1流量制御弁
436B :第2流量制御弁
PS1 :圧力センサ
PS2 :圧力センサ
PS3 :圧力センサ
PS4 :圧力センサ
Claims (15)
- 二酸化炭素回収システムであって、
二酸化炭素を含むガスが供給され、二酸化炭素を電解還元することによって、炭化水素、一酸化炭素、及び水素の少なくとも1つを含む生成ガスと未反応の二酸化炭素とを少なくとも含む混合ガスを生成する電解還元装置と、
前記混合ガスから二酸化炭素を分離する二酸化炭素分離装置とを有し、
前記二酸化炭素分離装置は、カソードである第1ガス拡散電極と、アノードである第2ガス拡散電極と、前記第1ガス拡散電極及び前記第2ガス拡散電極の間に形成され、酸化還元に伴ってプロトンを吸脱着する化合物を含む電解液が供給される液室と、前記第1ガス拡散電極によって前記液室に対して区画され、前記混合ガスが供給される第1室と、前記第2ガス拡散電極によって前記液室に対して区画され、前記混合ガスから分離された二酸化炭素が流れる第2室とを有し、
前記電解還元装置は、前記二酸化炭素分離装置において前記混合ガスから分離された二酸化炭素を原料の一部として使用する二酸化炭素回収システム。 - 前記二酸化炭素分離装置において二酸化炭素が分離された前記生成ガスから水を分離する少なくとも1つの水分除去装置と、
前記水分除去装置において水が分離された前記生成ガスを冷却することによって前記生成ガスから炭化水素を分離する生成ガス分離装置とを有する請求項1に記載の二酸化炭素回収システム。 - 前記生成ガス分離装置において炭化水素が分離された前記生成ガスであるオフガスの少なくとも一部を燃焼させる燃焼炉を有し、
前記水分除去装置は、水を吸着して水が分離された前記生成ガスを放出する吸着工程と、前記燃焼炉で発生した熱を受けて前記吸着工程において吸着した水を放出する脱離工程とを実行する請求項2に記載の二酸化炭素回収システム。 - 前記水分除去装置の前記脱離工程において放出される水を含むガスから液化した水を分離する第1気液分離装置と、
前記第1気液分離装置において水が分離されたガスを前記水分除去装置に戻す循環通路とを有し、
前記循環通路は前記燃焼炉と熱交換可能に配置されている請求項3に記載の二酸化炭素回収システム。 - 前記循環通路に、前記水分除去装置において水が分離された前記生成ガスの一部を供給する請求項4に記載の二酸化炭素回収システム。
- 前記燃焼炉において発生した、二酸化炭素及び水を含む排気を前記電解還元に供給する排ガス通路を有する請求項3に記載の二酸化炭素回収システム。
- 前記水分除去装置は、並列に2つ設けられ、一方の前記水分除去装置が前記吸着工程を実行しているときに他方の前記水分除去装置が前記脱離工程を実行する請求項3に記載の二酸化炭素回収システム。
- 前記二酸化炭素分離装置は、
前記二酸化炭素分離装置の前記第2室の入口及び出口に接続された二酸化炭素循環通路と、
前記二酸化炭素循環通路と前記電解還元装置のカソード室の入口とを接続する二酸化炭素戻し通路と、
前記二酸化炭素分離装置の前記第1室の入口と前記電解還元装置の前記カソード室の出口とを接続する混合ガス入口通路と、
前記二酸化炭素分離装置の前記第1室の出口に接続された生成ガス出口通路と、
前記液室の入口に電解液供給通路を介して接続されると共に、前記液室の出口に第1電解液戻し通路を介して接続された電解液タンクとを有する請求項1~7のいずれか1つの項に記載の二酸化炭素回収システム。 - 前記二酸化炭素循環通路に設けられた第2気液分離装置と、
前記第2気液分離装置において分離された液体を前記電解液タンクに第2電解液戻し通路と、
前記二酸化炭素戻し通路に設けられた第1圧力制御弁と、
前記混合ガス入口通路又は前記生成ガス出口通路に設けられた第2圧力制御弁と、
前記電解液供給通路又は前記第1電解液戻し通路に設けられた第3圧力制御弁と、
前記第1室の圧力を第1圧力として検出する第1圧力センサと、
前記第2室の圧力を第2圧力として検出する第2圧力センサと、
前記液室の圧力を第3圧力として検出する第3圧力センサと、
前記第1圧力が前記第3圧力以上になり、かつ前記第3圧力が前記第2圧力以上になるように、前記第1圧力制御弁、前記第2圧力制御弁、及び前記第3圧力制御弁を制御する制御装置とを有する請求項8に記載の二酸化炭素回収システム。 - 前記生成ガス出口通路において前記第1圧力制御弁よりも下流側に設けられた第4圧力制御弁と、
前記電解液タンクの頂部と前記生成ガス出口通路における前記第4圧力制御弁よりも上流側の部分とを接続するガス戻し通路と、
前記電解液タンクの圧力を第4圧力として検出する第4圧力センサとを有し、
前記制御装置は、前記第1圧力が前記第3圧力以上になり、かつ前記第3圧力が前記第4圧力以上になり、かつ前記第4圧力が前記第2圧力以上になるように、前記第1圧力制御弁、前記第2圧力制御弁、前記第3圧力制御弁、及び前記第4圧力制御弁を制御する請求項9に記載の二酸化炭素回収システム。 - 前記炭化水素がメタン及びエチレンの少なくとも1つを含む請求項1に記載の二酸化炭素回収システム。
- 酸化還元に伴ってプロトンを吸脱着する前記化合物が、pH7における標準水素電極電位基準での酸化還元電位が-1.0V~1.0Vの有機化合物である請求項1に記載の二酸化炭素回収システム。
- 酸化還元に伴ってプロトンを吸脱着する前記化合物が、キノン系化合物である請求項1に記載の二酸化炭素回収システム。
- 二酸化炭素回収システムであって、
二酸化炭素を含むガスが供給され、二酸化炭素を電解還元することによって、炭化水素、一酸化炭素、及び水素の少なくとも1つを含む生成ガスと未反応の二酸化炭素とを少なくとも含む混合ガスを生成する電解還元装置と、
前記混合ガスから二酸化炭素を分離する二酸化炭素分離装置とを有し、
前記二酸化炭素分離装置は、
酸化還元に伴ってプロトンを吸脱着する化合物を含む電解液と前記混合ガスとを接触させ、前記電解液に前記混合ガス中の二酸化炭素を吸収させる二酸化炭素ガス吸収部と、
電解質膜と、前記電解質膜の両面に設けられ、電源に接続されたカソード及びアノードとを含む膜電極複合体によってカソード室及びアノード室に区画された電気化学セルと、
前記電解液を前記二酸化炭素ガス吸収部から前記アノード室に流す第1通路と、
前記電解液を前記アノード室から前記カソード室に流す第2通路と、
前記電解液を前記カソード室から前記二酸化炭素ガス吸収部に流す第3通路と、
前記第2通路に設けられ、前記電解液中と二酸化炭素ガスとを分離する気液分離装置とを有し、
前記電解還元装置は、前記二酸化炭素分離装置において前記混合ガスから分離された二酸化炭素を原料の一部として使用する二酸化炭素回収システム。 - 前記二酸化炭素ガス吸収部は、上下に延び、底部に前記電解液を貯留するハウジングと、前記ハウジングの下部に設けられ、前記混合ガスが供給されるガス入口と、前記ハウジングの上端に設けられ、前記混合ガスが排出されるガス出口と、前記ハウジングの上部に設けられ、前記電解液を噴射するノズルと、前記ハウジングの前記底部に貯留された前記電解液を前記ノズルに供給する第4通路と、前記ハウジングにおいて前記ガス入口と前記ノズルとの間に設けられ、前記ノズルから供給された前記電解液を一時的に貯留するトレイと、前記トレイに設けられた電解液出口とを有し、
前記電解液出口は前記第1通路に接続され、
前記第3通路は前記第4通路に接続され、
前記第3通路には第1流量制御弁が設けられ、
前記第4通路における前記第3通路よりも前記ハウジングの前記底部側には第2流量制御弁が設けられ、
前記電源、前記第1流量制御弁、及び前記第2流量制御弁は制御装置によって制御され、
前記ハウジングの前記底部に貯留された前記電解液のpHをpH1、前記第4通路における前記第3通路よりも前記ノズル側の部分を流れる前記電解液のpHをpH2、前記第3通路を流れる前記電解液のpHをpH3、前記第1通路を流れる前記電解液のpHをpH4とすると、
前記制御装置は、pH3≧pH2≧pH1≧pH4≧5.5を満たすように、前記電源、前記第1流量制御弁、及び前記第2流量制御弁を制御する請求項14に記載の二酸化炭素回収システム。
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