WO2024261942A1 - メタネーションシステム - Google Patents

メタネーションシステム Download PDF

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Publication number
WO2024261942A1
WO2024261942A1 PCT/JP2023/023063 JP2023023063W WO2024261942A1 WO 2024261942 A1 WO2024261942 A1 WO 2024261942A1 JP 2023023063 W JP2023023063 W JP 2023023063W WO 2024261942 A1 WO2024261942 A1 WO 2024261942A1
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WO
WIPO (PCT)
Prior art keywords
cooling water
methane
water
separation membrane
methanation system
Prior art date
Application number
PCT/JP2023/023063
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English (en)
French (fr)
Japanese (ja)
Inventor
誠 川本
俊雄 篠木
洋次 尾中
誠 谷島
Original Assignee
三菱電機株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 三菱電機株式会社 filed Critical 三菱電機株式会社
Priority to JP2023574770A priority Critical patent/JP7580638B1/ja
Priority to PCT/JP2023/023063 priority patent/WO2024261942A1/ja
Publication of WO2024261942A1 publication Critical patent/WO2024261942A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/10—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with water vapour
    • 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

Definitions

  • This disclosure relates to a methanation system.
  • Patent Document 1 discloses an apparatus for producing hydrocarbons such as methane using carbon dioxide and water.
  • carbon dioxide supplied from the supply path 10 and water (raw water) supplied from the cooling water path 50 are supplied to the cathode electrode of the solid oxide electrolysis cell.
  • the water used for co-electrolysis in the solid oxide electrolysis cell is, for example, water vapor.
  • co-electrolysis can be performed using electricity obtained using renewable energy (e.g., solar power generation, wind power generation, etc.).
  • renewable energy e.g., solar power generation, wind power generation, etc.
  • this electricity is described as "electricity derived from renewable energy.”
  • Methane obtained using renewable energy can be considered a carbon-neutral fuel that does not affect global warming because no additional carbon dioxide is generated when it is burned.
  • a product gas containing methane (CH 4 ) and water (H 2 O) is obtained from carbon monoxide (CO) and hydrogen (H 2 ) through a methanation reaction.
  • the methanation reaction proceeds, for example, according to the following formula (II). This reaction is an exothermic reaction. CO+ 3H2 ⁇ CH4 + H2O ...(II)
  • the methane reactor 30 preferably includes a methanation catalyst with which the reactant gas comes into contact.
  • the methanation catalyst include Ni catalysts and Ru catalysts.
  • the methanation catalyst promotes the methanation reaction.
  • the product gas obtained in the methane reactor 30 is sent to the separation membrane device 40 via the communication path 12.
  • the water contained in the product gas is, for example, water vapor (steam).
  • the temperature of the product gas sent to the separation membrane device 40 is, for example, 100° C. to 400° C.
  • the product gas may contain not only methane and water but also other components such as unreacted carbon monoxide, hydrogen (H 2 ), carbon dioxide, etc.
  • the separation membrane device 40 separates a specific component from other components, for example, by using a separation membrane 41 that allows low molecular weight components to permeate.
  • the separation membrane 41 is, for example, a carbon membrane.
  • the carbon membrane is made of a carbon material.
  • the carbon membrane exhibits gas separation performance, for example, by the molecular sieve effect that utilizes micropores. By using a carbon membrane, it is possible to increase the efficiency of separating methane and water.
  • the separation membrane 41 may be an inorganic membrane made of an inorganic material.
  • the inorganic membrane is, for example, a metal membrane.
  • the separation membrane device 40 may be a separation membrane module in which the separation membrane 41 is housed in a case.
  • the separation membrane module may be a hollow fiber membrane module, a spiral membrane module, a flat membrane module, or the like.
  • the separation membrane 41 is formed in a hollow fiber membrane shape.
  • the separation membrane 41 has a spiral structure.
  • the spiral structure is a structure in which the separation membranes 41 are wound in a spiral shape and stacked on top of each other.
  • the separation membrane 41 is formed in a flat membrane shape.
  • the filtration method of the separation membrane device 40 may be a cross-flow filtration method or a total amount filtration method.
  • the supply side of the separation membrane 41 may be pressurized to increase the pressure.
  • low molecular weight components such as water from the product gas containing methane and water can be separated into components containing methane and components containing water by permeating the separation membrane 41.
  • the separation membrane 41 separates methane from water.
  • the water separated by the separation membrane 41 is "separated water.”
  • the permeate (permeate gas) that permeates the separation membrane 41 contains water (separated water).
  • the permeate is introduced to the ejector 70 by the introduction path 60.
  • the water (separated water) is, for example, steam.
  • the components that do not permeate the separation membrane 41 include methane.
  • the non-permeated components are discharged to the outside of the system through the discharge path 13.
  • the non-permeated components can be used, for example, as a raw material for city gas, etc.
  • the cooling water path 50 cools the reactant gas and product gas inside the methane reactor 30 by cooling water flowing through the flow passage 51.
  • the cooling water is heated by heat exchange with the methane reactor 30.
  • At least a portion of the cooling water is vaporized from a liquid state by heat exchange with the methane reactor 30 to become water vapor.
  • at least a portion of the cooling water is vaporized while flowing through the flow passage 51 from the inlet 51a to the outlet 51b.
  • the cooling water can cool the methane reactor 30 by the heat of vaporization that accompanies the vaporization. Therefore, the latent heat of the cooling water can be used to cool the methane reactor 30. Therefore, the amount of heat removed per heat transfer area of the cooling water passage 50 is increased. This allows the methane reactor 30 to be made smaller.
  • the cooling water passage 50 is connected to the co-electrolysis device 20.
  • the cooling water passage 50 supplies the cooling water that has passed through the methane reactor 30 and the separated water introduced from the introduction passage 60 to the co-electrolysis device 20 as raw water.
  • the ejector 70 is provided in the cooling water path 50.
  • the ejector 70 uses the cooling water that has passed through the methane reactor 30 as a driving flow to draw in the separated water through the inlet path 60.
  • the ejector 70 can draw in the separated water through the inlet path 60, for example, using the water vapor generated by heating the cooling water in the methane reactor 30 as a driving flow.
  • the ejector 70 guides the separated water to the cooling water path 50.
  • the use of the ejector 70 allows the pressure on the permeate side of the separation membrane device 40 to be lowered, eliminating the need to set the pressure on the supply side high.
  • the energy required for pressurization in the separation membrane device 40 can be reduced, improving the energy efficiency of the methanation system 100.
  • the ejector 70 draws in the separated water using the steam generated by the cooling water being heated by the methane reactor 30 as the driving force.
  • the cooling water becomes steam and its volume increases, increasing the flow rate, providing sufficient suction force. Therefore, the separated water can be led to the cooling water path 50 through the inlet path 60 without using power. This improves the energy efficiency of the methanation system 100.
  • Using a carbon membrane as the separation membrane 41 in the separation membrane device 40 can increase the efficiency of separating methane and water.
  • Embodiment 2. 2 is a schematic diagram of a methanation system 200 according to embodiment 2. Note that the same components as those in embodiment 1 are denoted by the same reference numerals and will not be described.
  • the methanation system 200 includes a methane reactor 230 instead of the methane reactor 30.
  • the methanation system 200 includes a cooling water path 250 instead of the cooling water path 50.
  • the methanation system 200 differs from the methanation system 100 shown in FIG. 1.
  • reactant gas containing carbon monoxide and hydrogen is obtained from carbon dioxide and water by co-electrolysis.
  • the reactant gas is sent to the methane reactor 230 via the communication path 11.
  • a reaction (methanation reaction) to obtain methane and water from carbon monoxide and hydrogen partially proceeds in the first methane reaction section 231 of the methane reactor 230.
  • the intermediate gas containing unreacted matter is supplied to the second methane reaction section 232 via the communication path 15.
  • a methanation reaction of the unreacted matter contained in the intermediate gas proceeds.
  • the methanation reaction proceeds in multiple stages (two stages in this embodiment).
  • the intermediate heat exchanger 233 is provided between the first methane reaction section 231 and the second methane reaction section 232.
  • the intermediate heat exchanger 233 is provided in the communication path 15.
  • the flow passage 251 which is part of the cooling water path 250, is thermally connected to the intermediate heat exchanger 233.
  • the flow passage 251 is disposed, for example, inside the intermediate heat exchanger 233.
  • the cooling water path 250 cools the intermediate gas in the intermediate heat exchanger 233 by the cooling water flowing through the flow passage 251.
  • the cooling water is vaporized into water vapor, for example, by heat exchange with the intermediate heat exchanger 233.
  • the cooling water can cool the intermediate heat exchanger 233 by the heat of vaporization that accompanies the vaporization. Therefore, the latent heat of the cooling water can be used to cool the intermediate heat exchanger 233. This increases the amount of heat removal per heat transfer area of the cooling water path 250. This allows the intermediate heat exchanger 233 to be made smaller.
  • the product gas obtained in the methane reactor 230 is sent to the separation membrane device 40 via the connection path 12.
  • the separation membrane device 40 separates the product gas into a component containing methane and a component containing water.
  • the non-permeated component containing methane is discharged through the discharge path 13.
  • the permeate containing the separated water is discharged through the introduction path 60.
  • the ejector 70 uses the cooling water that has passed through the methane reactor 230 as a driving flow to suck in the separated water through the inlet path 60.
  • the ejector 70 guides the separated water to the cooling water path 250.
  • the cooling water path 250 supplies the cooling water that has passed through the methane reactor 230 and the separated water guided from the inlet path 60 to the co-electrolysis device 20 as raw water.
  • the methanation system 200 similar to the methanation system 100 shown in FIG. 1, heat generated in the methane reactor 230 is recovered by cooling water and supplied to the co-electrolysis device 20. Therefore, in the co-electrolysis device 20, the efficiency of the electrolysis reaction can be increased while suppressing the energy required for heating. Therefore, the energy efficiency when producing methane can be increased.
  • the intermediate gas is cooled by cooling water in the intermediate heat exchanger 233, so the temperature in the second methane reaction section 232 can be kept within an appropriate range. This makes it possible to increase the efficiency of the methanation reaction in the second methane reaction section 232. This makes it possible to improve the methane yield in the methane reactor 230.
  • the heat of the intermediate gas is recovered by cooling water in the intermediate heat exchanger 233, so energy efficiency can be increased.
  • Embodiment 3. 3 is a schematic diagram of a methanation system 300 according to embodiment 3. Note that components common to other embodiments are given the same reference numerals and descriptions thereof will be omitted.
  • the methanation system 300 differs from the methanation system 100 shown in FIG. 1 in that it includes a circulation path 80.
  • the methanation system 300 may have the same configuration as the methanation system 100 shown in FIG. 1, except that it includes the circulation path 80.
  • the circulation path 80 connects the introduction path 60 and the connection path 12.
  • the circulation path 80 is provided with a flow control valve 81 (flow regulator) and a compressor 82.
  • the flow control valve 81 can adjust the flow rate of the permeate flowing through the circulation path 80 by adjusting the opening degree.
  • the compressor 82 increases the pressure of the permeate.
  • a reactant gas containing carbon monoxide and hydrogen is obtained from carbon dioxide and water by co-electrolysis.
  • the reactant gas is sent to the methane reactor 30 via the communication path 11.
  • a product gas containing methane and water is obtained by a methanation reaction.
  • the cooling water passage 50 guides the cooling water that cools the methane reactor 30.
  • the cooling water passage 50 cools the reactant gas and product gas inside the methane reactor 30 by the cooling water flowing through the flow passage 51.
  • the cooling water is heated by heat exchange with the methane reactor 30.
  • the product gas obtained in the methane reactor 30 is sent to the separation membrane device 40 via the connection path 12.
  • the separation membrane device 40 separates the product gas into a component containing methane and a component containing water.
  • the non-permeated component containing methane is discharged through the discharge path 13.
  • the permeate containing the separated water is discharged through the introduction path 60.
  • the ejector 70 uses the cooling water that has passed through the methane reactor 30 as a driving flow to suck in the separated water through the inlet path 60.
  • the ejector 70 guides the separated water to the cooling water path 50.
  • the cooling water path 50 supplies the cooling water that has passed through the methane reactor 30 and the separated water guided from the inlet path 60 to the co-electrolysis device 20 as raw water.
  • the methanation system 300 similar to the methanation system 100 shown in FIG. 1, heat generated in the methane reactor 30 is recovered by cooling water and supplied to the co-electrolysis device 20. Therefore, in the co-electrolysis device 20, the efficiency of the electrolysis reaction can be increased while suppressing the energy required for heating. Therefore, the energy efficiency when producing methane can be increased.
  • the circulation path 80 returns a portion of the permeate that has permeated the separation membrane 41 to the separation membrane device 40 via the connection path 12. This allows the methane contained in the permeate to be recovered. This increases the methane yield.
  • the methanation system 300 is provided with a flow rate control valve 81 in the circulation path 80, so the amount of permeate circulated in the circulation path 80 can be determined as desired. This allows the methanation system 300 to be operated with high precision.
  • Embodiment 4. 4 is a schematic diagram of a methanation system 400 according to embodiment 4. Note that components common to other embodiments are given the same reference numerals and descriptions thereof will be omitted.
  • the methanation system 400 includes a supply path 10, a co-electrolysis device 20, a methane reactor 30, a water separation device 440, a cooling water path 50, an introduction path 60, and multiple ejectors 70.
  • the water separation device 440 includes a plurality of separation membrane devices 40.
  • the water separation device 440 includes two separation membrane devices 40.
  • One of the two separation membrane devices 40 is a first separation membrane device 40A.
  • the other of the two separation membrane devices 40 is a second separation membrane device 40B.
  • the first separation membrane device 40A and the second separation membrane device 40B are connected via a connection path 16.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
PCT/JP2023/023063 2023-06-22 2023-06-22 メタネーションシステム WO2024261942A1 (ja)

Priority Applications (2)

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JP2023574770A JP7580638B1 (ja) 2023-06-22 2023-06-22 メタネーションシステム
PCT/JP2023/023063 WO2024261942A1 (ja) 2023-06-22 2023-06-22 メタネーションシステム

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PCT/JP2023/023063 WO2024261942A1 (ja) 2023-06-22 2023-06-22 メタネーションシステム

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4878105A (enrdf_load_stackoverflow) * 1972-01-24 1973-10-20
US4839391A (en) * 1986-04-16 1989-06-13 Kernforschungsanlage Julich Gmbh Method and reactor for catalytic methanization of a gas containing CO, CO2 and H2
US20120148481A1 (en) * 2009-08-03 2012-06-14 Clomburg Jr Lloyd Anthony Process for the co-production of superheated steam and methane
JP2014198789A (ja) * 2013-03-29 2014-10-23 大阪瓦斯株式会社 メタンリッチガス製造システム
US20150080483A1 (en) * 2012-04-10 2015-03-19 Siemens Aktiengesellschaft Power station-based methanation system
JP2016108256A (ja) * 2014-12-03 2016-06-20 三菱化学株式会社 メタン及び水素の併産方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0647060B2 (ja) * 1985-08-16 1994-06-22 三菱化成株式会社 水蒸気の分離法
JPH0763579B2 (ja) * 1988-10-06 1995-07-12 三菱化学株式会社 脱湿方法
JP7523321B2 (ja) * 2020-11-06 2024-07-26 大阪瓦斯株式会社 燃料ガスの製造方法
JP2023098433A (ja) * 2021-12-28 2023-07-10 株式会社日立製作所 メタネーションシステム
WO2023233494A1 (ja) * 2022-05-31 2023-12-07 三菱電機株式会社 メタン生成システム

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4878105A (enrdf_load_stackoverflow) * 1972-01-24 1973-10-20
US4839391A (en) * 1986-04-16 1989-06-13 Kernforschungsanlage Julich Gmbh Method and reactor for catalytic methanization of a gas containing CO, CO2 and H2
US20120148481A1 (en) * 2009-08-03 2012-06-14 Clomburg Jr Lloyd Anthony Process for the co-production of superheated steam and methane
US20150080483A1 (en) * 2012-04-10 2015-03-19 Siemens Aktiengesellschaft Power station-based methanation system
JP2014198789A (ja) * 2013-03-29 2014-10-23 大阪瓦斯株式会社 メタンリッチガス製造システム
JP2016108256A (ja) * 2014-12-03 2016-06-20 三菱化学株式会社 メタン及び水素の併産方法

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
ANONYMOUS: "Cooling water has its types and characteristics! Why use water for cooling? ", TAIYO ALESCO CO., LTD. HOMEPAGE., 4 August 2021 (2021-08-04), XP093252748, Retrieved from the Internet <URL:https://www.taiyoalesco.jp/blog/1687> *
KITA HIDETOSHI: "Outlook for Gas Separation Membranes", MEMBRANE, vol. 33, no. 5, 1 January 2008 (2008-01-01), pages 247 - 253, XP093252746, DOI: 10.5360/membrane.33.247 *
OKAMOTO, KENICHI: "Gas Separation Membranes", JOURNAL OF THE TEXTILE MACHINERY SOCIETY OF JAPAN, vol. 43, no. 9, 25 September 1990 (1990-09-25), pages 501 - 508, XP093252737, DOI: 10.4188/transjtmsj.43.9_P501 *

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JP7580638B1 (ja) 2024-11-11

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