Methane Synthesis System

The methane synthesis system addresses low efficiency in methane production by using a co-electrolysis unit and cooling unit to optimize reaction temperatures, enhancing energy efficiency and methane yield.

JP7761630B2Active Publication Date: 2025-10-28MITSUBISHI ELECTRIC CORP
View PDF 9 Cites 0 Cited by

Patent Information

Application Number
JP2023505685
Authority / Receiving Office
JP · JP
Patent Type
Patents
Current Assignee / Owner
Filing Date
2022-07-15
Publication Date
2025-10-28
Estimated Expiration
2042-07-15

AI Technical Summary

Technical Problem

Existing methane production systems exhibit low efficiency in producing methane from carbon dioxide and water.

Method used

A methane synthesis system comprising a co-electrolysis unit to produce hydrogen and carbon monoxide from water and carbon dioxide, a methanation reaction unit to convert these gases into methane, and a cooling unit using a phase-changeable refrigerant to optimize reaction temperatures through vaporization heat.

Benefits of technology

Enhances methane production efficiency by optimizing reaction temperatures and effectively utilizing energy, resulting in improved energy efficiency and increased methane yield.

✦ Generated by Eureka AI based on patent content.

Smart Images

  • Figure 0007761630000001
    Figure 0007761630000001
  • Figure 0007761630000002
    Figure 0007761630000002
  • Figure 0007761630000003
    Figure 0007761630000003
Patent Text Reader

Abstract

A methane synthesis system according to the present disclosure comprises: a co-electrolysis unit that obtains hydrogen and carbon monoxide from water and carbon dioxide through electrolysis; a methanation reaction unit that obtains a product gas containing methane through a methanation reaction using the hydrogen and the carbon monoxide; and a cooling unit that has a flow channel through which a phase-changeable coolant flows. The cooling unit cools the methanation reaction unit by vaporization heat which is associated with vaporization of at least a portion of the coolant within the flow channel.
Need to check novelty before this filing date? Find Prior Art

Description

[Technical Field]

[0001] The present disclosure relates to a methane synthesis system. [Background technology]

[0002] Patent Document 1 discloses a production system for producing hydrocarbons using carbon dioxide and water. This production system reduces water and carbon dioxide to obtain a mixed gas containing hydrogen and carbon monoxide. This production system generates hydrocarbons such as methane from the mixed gas. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 2021 / 201192 Summary of the Invention [Problem to be solved by the invention]

[0004] This technique may result in low methane production efficiency.

[0005] In view of the above circumstances, an object of the present disclosure is to provide a methane synthesis system that can increase the efficiency of methane production. [Means for solving the problem]

[0006] One aspect of the methane synthesis system according to the present disclosure comprises a co-electrolysis unit that obtains hydrogen and carbon monoxide from water and carbon dioxide by electrolysis, a methanation reaction unit that obtains a product gas containing methane by a methanation reaction using the hydrogen and the carbon monoxide, and a cooling unit having a flow passage through which a phase-changeable refrigerant flows. The cooling unit cools the methanation reaction unit by heat of vaporization associated with vaporization of at least a portion of the refrigerant in the flow passage. [Effects of the Invention]

[0007] According to the present disclosure, a methane synthesis system capable of increasing the efficiency of methane production can be provided. [Brief explanation of the drawings]

[0008] [Figure 1] 1 is a schematic diagram of a methane synthesis system according to a first embodiment. [Figure 2] FIG. 10 is a schematic diagram of a methane synthesis system according to a second embodiment. [Figure 3] FIG. 10 is a schematic diagram of a methane synthesis system according to a third embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0009] Hereinafter, embodiments of the present disclosure will be described with reference to the drawings. Note that the scope of the present disclosure is not limited to the following embodiments and can be modified as desired within the scope of the technical concept of the present disclosure.

[0010] Embodiment 1 FIG. 1 is a schematic diagram showing a methane synthesis system according to the first embodiment. As shown in FIG. 1, the methane synthesis system 1 includes a supply path 2, a co-electrolysis section 3, a methanation reaction section 4, a cooling section 5, a separator 6, a recovery path 7, a first heat exchanger 8, and an ejector 9.

[0011] The supply path 2 introduces water (for example, water vapor) and carbon dioxide to the co-electrolysis unit 3. The water (for example, water vapor) is supplied from the cooling unit 5. The carbon dioxide is supplied from the introduction path 11. The supply path 2 introduces, for example, a mixed fluid of water and carbon dioxide to the co-electrolysis unit 3.

[0012] The carbon dioxide supplied from the introduction path 11 may be carbon dioxide captured from the atmosphere by DAC (Direct Air Capture), or may be carbon dioxide exhausted from a solid oxide fuel cell (SOFC).

[0013] The co-electrolysis unit 3 includes, for example, a solid oxide electrolysis cell (SOEC) having a cathode electrode and an anode electrode. The solid oxide electrolysis cell uses, for example, a solid oxide having oxygen ion conductivity. A zirconia-based oxide or the like is used as the electrolyte. The co-electrolysis unit 3 is an example of an electrolysis device.

[0014] The co-electrolysis unit 3 supplies the water and carbon dioxide supplied from the supply path 2 to the cathode electrode of the solid oxide electrolysis cell. The water used for co-electrolysis in the solid oxide electrolysis cell is preferably water vapor.

[0015] The co-electrolysis unit 3 may include a heating device that heats the solid oxide electrolysis cell. The heating device can adjust the temperature inside the solid oxide electrolysis cell to a temperature suitable for the co-electrolysis reaction. The ratio of carbon dioxide and water supplied to the solid oxide electrolysis cell can be determined according to the ratio of the components (carbon monoxide, hydrogen) of the target mixed gas.

[0016] The co-electrolysis unit 3 obtains a mixed gas (mixed fluid) containing hydrogen (H) and carbon monoxide (CO) from water (H2O) and carbon dioxide (CO2) by co-electrolysis. Co-electrolysis proceeds, for example, according to the following formula (I). This reaction is an endothermic reaction. Co-electrolysis is an electrolysis reaction in which the electrolysis of water and the electrolysis of carbon dioxide are carried out simultaneously. 3H2O+CO2→CO+3H2+2O2···(I)

[0017] In the co-electrolysis unit 3, co-electrolysis can be performed using, for example, electricity generated using renewable energy (for example, solar power generation, wind power generation, etc.). Methane obtained using renewable energy can be considered a carbon-neutral fuel that does not contribute to global warming because no additional carbon dioxide is generated when it is combusted.

[0018] The mixed gas obtained in the co-electrolysis unit 3 contains not only hydrogen (H2) and carbon monoxide, but also unreacted water and carbon dioxide. The mixed gas is led to the methanation unit 4 through the lead-out line 12.

[0019] The methanation reaction section 4 obtains a product gas (product fluid) containing water (H2O) and methane (CH4) from hydrogen (H2) and carbon monoxide (CO) through a methanation reaction. The methanation reaction proceeds, for example, according to the following formula (II). This reaction is an exothermic reaction. 3H2+CO→H2O+CH4 (II)

[0020] The methanation reaction section 4 preferably includes a methanation catalyst with which the mixed gas comes into contact. Examples of the methanation catalyst include a Ni catalyst and a Ru catalyst. The methanation catalyst promotes the methanation reaction.

[0021] The product gas obtained in the methanation reaction section 4 may contain not only water and methane, but also unreacted hydrogen (H2), carbon monoxide, carbon dioxide, etc. The product gas is led to the separator 6 through a discharge line 13. An inlet 4a of the methanation reaction section 4 is connected to the outlet line 12. An outlet 4b of the methanation reaction section 4 is connected to the discharge line 13.

[0022] The cooling section 5 is thermally connected to the methanation reaction section 4. For example, the cooling section 5 is in contact with the methanation reaction section 4. For example, the cooling section 5 is formed integrally with the methanation reaction section 4. Heat can be transferred between the cooling section 5 and the methanation reaction section 4.

[0023] The cooling section 5 cools the methanation reaction section 4. A flow passage 51 through which a refrigerant flows is formed in the cooling section 5. The flow direction of the refrigerant in the flow passage 51 (direction from the inlet 51a to the outlet 51b) is, for example, opposite to the flow direction in the methanation reaction section 4 (direction from the inlet 4a to the outlet 4b).

[0024] Separator 6 separates a methane-containing fluid and a water-containing fluid from the product gas. Separation techniques such as liquefaction separation, membrane separation, and adsorption separation are employed in the separator 6. The separator 6 may employ one of these separation techniques, or a combination of two or more of them.

[0025] The separator 6 using liquefaction separation liquefies a specific component and separates it from other components (gases), for example. Specifically, for example, a component containing water is liquefied by temperature adjustment and separated from other components (gases) containing methane.

[0026] The membrane separator 6 separates a specific component from other components using, for example, a separation membrane that allows small molecular components to pass through. Specifically, for example, a separation membrane that selectively allows water to pass through is used. This separation membrane separates the component containing water from the other components, including methane, from the mixed gas.

[0027] Separator 6 using adsorption separation separates specific components by, for example, adsorbing them onto an adsorbent. Examples of adsorbents include silica gel, zeolite, and activated carbon. Specifically, by adsorbing a component containing water onto an adsorbent, this component can be separated from other components containing methane.

[0028] The separator 6 using adsorption separation has the function of desorbing the adsorbates from the adsorbent. The separator 6 is equipped with, for example, a heating device. The heating device heats the adsorbent to desorb the adsorbates from the adsorbent. The separator 6 may also be equipped with a pressure reducing device such as a vacuum pump. The pressure reducing device places the adsorbent under reduced pressure to promote desorption of the adsorbates from the adsorbent.

[0029] The methane-containing component is discharged from the separator 6 through a discharge line 14. The methane-containing component is sent to a gas production facility or the like as a raw material for city gas or the like, for example.

[0030] The recovery path 7 connects the separator 6 and the cooling unit 5. The component containing water (water-containing fluid F1) is discharged from the separator 6 through the recovery path 7 and introduced into the flow path 51 of the cooling unit 5. The recovery path 7 is provided with a pump 71 for sending the fluid F1 to the cooling unit 5. The main component of the fluid F1 is water. The fluid F1 can change phases between liquid and gas. The fluid F1 may contain other components in addition to water.

[0031] A water supply path 15 is connected to the recovery path 7. Water is supplied to the recovery path 7 from the outside via the water supply path 15 as needed.

[0032] The first heat exchanger 8 is provided in the recovery line 7. The first heat exchanger 8 preheats the fluid F1 flowing through the recovery line 7 by heat exchange with the product gas flowing through the discharge line 13. A known heat exchanger can be used as the first heat exchanger 8. For example, a shell-and-tube heat exchanger, a plate heat exchanger, a coil heat exchanger, a double-pipe heat exchanger, a spiral heat exchanger, or the like can be used as the first heat exchanger 8.

[0033] The fluid F1 flowing through the recovery line 7 is introduced into the flow passage 51 of the cooling section 5, and flows as a coolant through the flow passage 51. The methanation reaction section 4 is cooled by heat exchange with the fluid F1.

[0034] At least a part of the fluid F1 is liquid at the inlet 51a of the flow passage 51. At least a part of the fluid F1 vaporizes while flowing through the flow passage 51 from the inlet 51a to the outlet 51b. When the fluid F1 vaporizes, the methanation reaction section 4 is cooled by the heat of vaporization.

[0035] The ejector 9 is provided in the supply path 2. The ejector 9 has an inlet 9a, a suction port 9b, and an outlet 9c. The fluid F1 flowing through the supply path 2 flows into the ejector 9 from the inlet 9a and flows out from the outlet 9c. The fluid F1 serves as a driving fluid. A nozzle for ejecting the driving fluid is provided inside the ejector 9. An introduction path 11 is connected to the suction port 9b. Carbon dioxide flows into the ejector 9 as a suction fluid from the suction port 9b through the introduction path 11.

[0036] Next, an example of a methane synthesis method using the methane synthesis system 1 will be described. The methane synthesis method according to this embodiment includes a supplying step, an electrolysis step, a methanation step, a separation step, and a cooling step.

[0037] In the supply step, water (H2O) and carbon dioxide (CO2) are introduced into the co-electrolysis section 3 through the supply path 2. In the electrolysis step, in the co-electrolysis section 3, a mixed gas containing hydrogen (H2) and carbon monoxide (CO) is obtained from water and carbon dioxide by co-electrolysis.

[0038] In the methanation step, a product gas containing water and methane is obtained from hydrogen and carbon monoxide by a methanation reaction in methanation reaction section 4. The product gas contains not only water and methane but also unreacted carbon monoxide, hydrogen (H2), carbon dioxide, etc. The product gas is led to separator 6 through discharge path 13.

[0039] In the separation step, a fluid containing methane and a fluid containing water are separated from the product gas in separator 6.

[0040] In the cooling step, the water-containing fluid F1 is led out of the separator 6 and introduced into the flow passage 51 of the cooling unit 5 via the recovery line 7. The fluid F1 acts as a refrigerant and is at least partially vaporized while flowing through the flow passage 51 from the inlet 51a to the outlet 51b. When vaporized, the fluid F1 cools the methanation reaction unit 4 by the heat of vaporization.

[0041] The cooling section 5 forms a temperature distribution having a first region, a second region, and a third region in this order from the inlet 51a to the outlet 51b of the flow passage 51. The first region is a region where the temperature of the fluid F1 increases. The second region is a region where the temperature of the fluid F1 remains approximately constant while vaporizing. The third region is a region where the temperature of the vaporized fluid F1 increases again. The temperature of the fluid F1 at the inlet 51a of the flow path 51 is lower than the temperature of the fluid F1 at the outlet 51b. The temperature of the fluid F1 at the inlet 51a is, for example, 200°C to 400°C. The temperature of the fluid F1 at the outlet 51b is, for example, 450°C to 650°C.

[0042] The temperature of the methanation reaction section 4 depends on the cooling section 5. That is, the temperature at the outlet 4b is lower than the temperature at the inlet 4a. The temperature in the methanation reaction section 4 at the outlet 4b is, for example, 200°C to 400°C. The temperature in the methanation reaction section 4 at the inlet 4a is, for example, 450°C to 650°C.

[0043] A fluid F1 containing water (water vapor) is introduced into the co-electrolysis section 3 through a supply path 2 together with carbon dioxide introduced by an ejector 9.

[0044] In the methane synthesis system 1, the cooling section 5 cools the methanation reaction section 4 by the heat of vaporization that accompanies the vaporization of at least a portion of the fluid F1, which serves as a refrigerant, in the flow passage 51. For example, the cooling section 5 has a first region where the temperature of the fluid F1 increases, a second region where the temperature of the fluid F1 remains substantially constant while vaporizing, and a third region where the temperature of the vaporized fluid F1 increases again. In the methanation reaction section 4, the reaction heat of the methanation reaction is appropriately removed as heat of vaporization in the second region, thereby optimizing the temperature within the methanation reaction section 4. This allows the methanation reaction to proceed efficiently. This increases the efficiency of methane production.

[0045] In the methane synthesis system 1, the fluid F1 containing water is used as a coolant, so that an appropriate temperature distribution can be provided in the methanation reaction section 4. Therefore, the methanation reaction in the methanation reaction section 4 can proceed efficiently.

[0046] The methane synthesis system 1 includes the supply path 2 that guides the fluid F1 that has passed through the cooling unit 5 to the co-electrolysis unit 3, and therefore the heat gained by the fluid F1 in the cooling unit 5 can be effectively utilized in the co-electrolysis unit 3. This improves the energy efficiency of the entire system.

[0047] The methane synthesis system 1 includes the ejector 9, and therefore can save energy compared to, for example, a case in which carbon dioxide is introduced into the supply path 2 using only a blower.

[0048] The methane synthesis system 1 includes a separator 6 that separates a water-containing fluid F1 from the product gas of the methanation reaction, and a recovery path 7 that guides the fluid F1 to the cooling section 5. This makes it possible to effectively utilize water, which is a product of the methanation reaction, and to increase the efficiency of the methane synthesis system.

[0049] Embodiment 2 Next, a methane synthesis system according to embodiment 2 will be described. The basic configuration of the methane synthesis system according to this embodiment is similar to that of embodiment 1, so differences from embodiment 1 will mainly be described. The same components as those in other embodiments will be assigned the same reference numerals and descriptions thereof will be omitted.

[0050] FIG. 2 is a schematic diagram of a methane synthesis system according to the second embodiment. As shown in Fig. 2, the methane synthesis system 101 differs from the methane synthesis system 1 (see Fig. 1) in that it includes an outlet line 16 and a second heat exchanger 17. The second heat exchanger 17 is an example of a "heat exchanger".

[0051] In the co-electrolysis section 3, oxygen (O2) is produced at the anode by the co-electrolysis of water and carbon dioxide described above. The outlet path 16 discharges the fluid F2 containing oxygen (O2) generated in the co-electrolysis section 3.

[0052] The second heat exchanger 17 is provided in the recovery path 7. The second heat exchanger 17 heats the fluid F1 flowing through the recovery path 7 by heat exchange with the fluid F2 led out through the lead-out path 16. A known heat exchanger can be used as the second heat exchanger 17. For example, a shell-and-tube heat exchanger, a plate heat exchanger, a coil heat exchanger, a double-pipe heat exchanger, a spiral heat exchanger, or the like can be used as the second heat exchanger 17.

[0053] Similar to the methane synthesis system 1 (see FIG. 1), the methane synthesis system 101 can optimize the temperature in the methanation reaction section 4, thereby improving the efficiency of methane production. In addition, the methane synthesis system 101 exhibits the same effects as the methane synthesis system 1 (see FIG. 1).

[0054] The methane synthesis system 101 can preheat the fluid F1 by the second heat exchanger 17. Therefore, the heat of the fluid F2 can be effectively utilized, and the energy efficiency of the entire system can be improved.

[0055] Embodiment 3 A description will be given of a methane synthesis system according to embodiment 3. The same components as those in other embodiments will be given the same reference numerals and descriptions thereof will be omitted.

[0056] FIG. 3 is a schematic diagram of a methane synthesis system according to the third embodiment. As shown in FIG. 3, the methane synthesis system 201 differs from the methane synthesis system 1 (see FIG. 1) in that it includes a methane purifier 202 and a return line 203. The methane purifier 202 is provided in the outlet line 14. The outlet line 14 is a line that extracts a component containing methane (fluid F3 containing methane) from the separator 6. The methane purifier 202 purifies the methane contained in the fluid F3 to obtain a fluid F4 with a high methane concentration. The methane purifier 202 is an example of a "methane purification unit."

[0057] Purification methods that can be used in the methane purifier 202 include membrane separation, liquefaction separation, and adsorption separation, with membrane separation being preferred. The methane purifier 202 using membrane separation includes, for example, a separation membrane that selectively allows methane to permeate.

[0058] The return line 203 connects the non-permeate side outlet of the methane purifier 202 to the outlet line 12. The return line 203 returns the non-permeate side fluid F5, which has not permeated the separation membrane of the methane purifier 202, to the methanation reaction section 4 via the outlet line 12. The return line 203 may also be a line connecting the non-permeate side outlet of the methane purifier 202 to the methanation reaction section 4.

[0059] In the methane synthesis system 201, the fluid F3 discharged from the separator 6 through the discharge line 14 is introduced into the methane purifier 202. The permeate-side fluid F4, whose methane concentration has been increased by the methane purifier 202, is discharged to the outside of the system as a purified product gas (purified product fluid). The process of purifying the methane contained in the fluid F3 using the methane purifier 202 is referred to as the "purification process."

[0060] The non-permeated fluid F5 that has not permeated the separation membrane of the methane purifier 202 is returned to the outlet line 12 via the return line 203. The fluid F5 is introduced from the outlet line 12 into the methanation reaction section 4. This promotes methanation of unreacted substances (e.g., hydrogen, carbon monoxide) contained in the fluid F5. This increases the efficiency of methane production in the methanation reaction section 4. The non-permeate fluid F5 is a retentate gas (retentate fluid) obtained by separating the permeate fluid F4 from the fluid F3.

[0061] Similar to the methane synthesis system 1 (see FIG. 1), the methane synthesis system 201 can optimize the temperature in the methanation reaction section 4, thereby improving the efficiency of methane production. In addition, the methane synthesis system 201 exhibits the same effects as the methane synthesis system 1 (see FIG. 1).

[0062] The methane synthesis system 201 includes the methane purifier 202, and therefore, a fluid F4 (purified gas) having a high concentration of methane can be obtained. The methane synthesis system 201 has a return line 203, so that the non-permeated fluid F5 (residue gas) can be returned to the methanation reaction section 4. This makes it possible to increase the efficiency of methane production in the methanation reaction section 4.

[0063] The technical scope of the present disclosure is not limited to the above-described embodiments, and various modifications can be made without departing from the spirit of the present disclosure. For example, in the first embodiment, the co-electrolysis unit 3 uses a solid oxide electrolysis cell (SOEC), but other types may be adopted for the co-electrolysis unit. For example, the co-electrolysis unit may be a solid polymer type co-electrolysis unit.

[0064] In the first embodiment, a co-electrolysis unit 3 is used to obtain hydrogen and carbon monoxide from water and carbon dioxide by co-electrolysis, but the device for obtaining hydrogen (H2) and carbon monoxide is not limited to a co-electrolysis unit. For example, an electrolysis device that independently performs a step of electrolyzing carbon dioxide to obtain carbon monoxide and a step of electrolyzing water to obtain hydrogen (H2) may also be used. [Explanation of symbols]

[0065] 1,101,201...Methane synthesis system 2...Supply route 3...Co-electrolysis section 4...Methanation reaction section 4a...Inlet 4b...Outlet 5...Cooling section 6...Separator 7...Recovery route 9...Ejector 17...Second heat exchanger (heat exchanger) 202...Methane purifier (methane purification section) 203...Return route

Claims

1. a co-electrolysis section that obtains hydrogen and carbon monoxide from water and carbon dioxide by electrolysis; a methanation reaction section for obtaining a product gas containing methane by a methanation reaction using the hydrogen obtained from the co-electrolysis section and the carbon monoxide; a cooling section having a flow passage through which water as a phase-changeable refrigerant flows, the cooling section cooling the methanation reaction section; an introduction means for introducing the refrigerant from the outside of the cooling unit into the flow passage inside the cooling unit; Equipped with the cooling section is thermally connected to the methanation reaction section, and forms a first region in which the temperature of the refrigerant introduced from the outside by the introducing means increases, and a second region in which the temperature of the refrigerant becomes substantially constant by cooling the methanation reaction section with heat of vaporization associated with the refrigerant vaporizing in the flow passage after passing through the first region, and the temperature at the outlet of the methanation reaction section is made lower than the temperature at the inlet, The refrigerant that has passed through the cooling unit is led to the co-electrolysis unit as the water to be used in the electrolysis. Methane synthesis system.

2. a supply path for introducing the refrigerant that has passed through the cooling section into the co-electrolysis section as the water to be used in the electrolysis; The methane synthesis system according to claim 1 .

3. an ejector that uses the water as a driving fluid to suck in the carbon dioxide is provided in the supply path; The methane synthesis system according to claim 2 .

4. a separator for separating water from the product gas; A recovery path that guides the water separated by the separator to the cooling unit as the refrigerant. The methane synthesis system according to any one of claims 1 to 3.

5. a heat exchanger that heats the water by heat exchange with oxygen generated by co-electrolysis of the water and the carbon dioxide in the co-electrolysis unit is provided in the recovery path; The methane synthesis system according to claim 4.

6. a separator for separating the methane-containing fluid from the product gas; a methane purification unit that purifies the methane contained in the methane-containing fluid to obtain a purified product gas, The methane synthesis system according to any one of claims 1 to 3.

7. a return path for returning a residue gas obtained by separating the purified product gas from the methane-containing fluid to the methanation reaction section, The methane synthesis system according to claim 6.

Citation Information

Patent Citations

  • Process for preparing synthetic gas and apparutus and improvement in method of making methane

    JP1976118704A

  • Method and apparatus for methanizing raw material gas containing carbon monoxide and hydrogen

    JP1979115303A

  • Conversion and apparatus for gas by catalytic reaction

    JP1980024190A

  • Catalyst reaction device

    JP2020093216A

  • Hydrocarbon production system, method for producing the system, and method for operating the system

    JP2021161124A