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WO2022044481A1 - Procédé de séparation de co2, dispositif de séparation de co2 et système de combustion - Google Patents

Procédé de séparation de co2, dispositif de séparation de co2 et système de combustion Download PDF

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Publication number
WO2022044481A1
WO2022044481A1 PCT/JP2021/021826 JP2021021826W WO2022044481A1 WO 2022044481 A1 WO2022044481 A1 WO 2022044481A1 JP 2021021826 W JP2021021826 W JP 2021021826W WO 2022044481 A1 WO2022044481 A1 WO 2022044481A1
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Prior art keywords
separation membrane
treatment chamber
gas
separation
membrane module
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PCT/JP2021/021826
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English (en)
Japanese (ja)
Inventor
治 岡田
正明 寺本
伸彰 花井
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株式会社ルネッサンス・エナジー・リサーチ
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Priority to JP2022545458A priority Critical patent/JPWO2022044481A1/ja
Publication of WO2022044481A1 publication Critical patent/WO2022044481A1/fr

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    • 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
    • B01D53/22—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 diffusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/38—Liquid-membrane separation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/50—Carbon dioxide
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2

Definitions

  • the present invention comprises a CO 2 separation membrane containing CO 2 carriers that selectively react with carbon dioxide, and a first treatment chamber and a second treatment chamber separated by the CO 2 separation membrane.
  • a CO 2 separation method and device for separating carbon dioxide from a mixed gas containing specific gas, carbon dioxide, and water vapor that do not react with CO 2 carriers by using multiple stages connected in series further, with the CO 2 separation device.
  • a combustion system equipped with a combustion device Regarding
  • the non-permeable gas that did not permeate the CO 2 separation membrane is as follows. It is supplied as it is to the first processing chamber of the separation membrane module of the stage.
  • the non-permeable gas that did not permeate the CO 2 separation membrane is relative.
  • the humidity falls below a predetermined value, it is cooled to raise the relative humidity, and then supplied to the first processing chamber of the separation membrane module in the next stage.
  • the CO 2 separation membrane containing a CO 2 carrier functions as a CO 2 promoted transport membrane that selectively permeates CO 2 by the reaction between CO 2 and the CO 2 carrier by the accelerated transport mechanism.
  • the CO 2 permeation rate of the CO 2 accelerated transport film depends on the relative humidity of the mixed gas containing CO 2 and steam (H 2 O) supplied to the supply side of the CO 2 accelerated transport film, and the lower the relative humidity, the more CO 2 Permence is reduced.
  • the mixed gas is supplied to the CO 2 accelerated transport film, the permeation rate of steam is faster than the permeation rate of CO 2 , and the mixed gas is contained in the mixed gas along the flow direction of the mixed gas on the supply side of the CO 2 accelerated transport film. The amount of steam decreases and the relative humidity decreases.
  • Patent Document 2 in order to solve the above problem, the non-permeable gas discharged from the first treatment chamber of the separation membrane module is cooled to raise the relative humidity, and then the first separation membrane module of the next stage is used. It is supplied to the processing room.
  • the increase in the relative humidity is small, and there is a concern that the CO 2 permeance decreases due to the decrease in the temperature of the impermeable gas. It may not be possible to sufficiently suppress the decrease in carbon dioxide.
  • the CO 2 separation method according to the present invention for achieving the above object is Two or more stages of separation membrane modules including a CO 2 separation membrane containing CO 2 carriers that selectively react with carbon dioxide, and a first treatment chamber and a second treatment chamber separated by the CO 2 separation membrane.
  • a mixed gas containing a specific gas, carbon dioxide, and water vapor that does not react with the CO 2 carrier is supplied from one end side of the first treatment chamber to the first treatment chamber.
  • Carbon dioxide in the mixed gas supplied to the first treatment chamber is permeated to the second treatment chamber side through the CO 2 separation membrane to separate carbon dioxide from the mixed gas.
  • the non-permeated gas containing the specific gas, carbon dioxide, and water vapor remaining in the first treatment chamber without penetrating the CO 2 separation membrane is discharged from the other end side of the first treatment chamber.
  • the permeated gas that has permeated the CO 2 separation membrane containing the separated carbon dioxide is discharged to the outside from the same side as the other end side of the first treatment chamber of the second treatment chamber.
  • water vapor is added to the non-permeable gas discharged from the other end side of the first treatment chamber, and the mixing of the separation membrane module connected to the rear stage side.
  • the first feature is that the gas is supplied to the first processing chamber from the one end side of the first processing chamber of the separation membrane module on the subsequent stage side.
  • the CO 2 separation device for achieving the above object is Two or more stages of separation membrane modules including a CO 2 separation membrane containing CO 2 carriers that selectively react with carbon dioxide, and a first treatment chamber and a second treatment chamber separated by the CO 2 separation membrane. It has at least a series of separation membrane modules connected in series and a steam supply unit. Each stage of the separation membrane module A first inlet / outlet for supplying a mixed gas containing a specific gas, carbon dioxide, and water vapor that does not react with the CO 2 carrier to the first treatment chamber is provided on one end side of the first treatment chamber.
  • a first discharge port that discharges a non-permeable gas containing the specific gas, carbon dioxide, and water vapor remaining in the first treatment chamber without penetrating the CO 2 separation membrane. Equipped with A part of the specific gas, carbon dioxide, and water vapor in the mixed gas on the same side as the other end side of the first treatment chamber of the second treatment chamber, and said via the CO 2 separation membrane.
  • a second discharge port for discharging the permeated gas that has permeated from the first treatment chamber side to the second treatment chamber side is provided.
  • the first discharge port is interconnected with the first inlet / outlet of the separation membrane module connected to the rear stage side to form a connecting portion.
  • the steam supply section is configured to supply steam to each of the connecting sections.
  • the non-permeable gas discharged from the first discharge port and the water vapor supplied to the connecting portion are connected to the rear stage side of the separation membrane module.
  • the first feature is that the mixed gas is configured to be supplied to the first processing chamber from the first inlet / outlet of the separation membrane module on the subsequent stage side.
  • the non-permeated gas discharged from the other end side of the first treatment chamber is the non-permeated gas. It is preferable to add water vapor so that the relative humidity of the module increases by 20% or more.
  • the steam supply unit is relative to the non-permeable gas discharged from the first discharge port with respect to each stage of the separation membrane module other than the final stage. It is preferable to supply water vapor to the connecting portion so that the humidity increases by 20% or more.
  • the relative humidity of the mixed gas to be supplied to the first processing chamber of the separation membrane module of the first stage is less than 70%, the said. It is preferable to supply water vapor so that the relative humidity is 70% or more.
  • the mixed gas supplied to the first treatment chamber of the separation membrane module in the first stage is derived from the biogas produced by methane fermentation of an organic substance.
  • the second feature is that the specific gas is methane.
  • the methane concentration in the dry base in the impermeable gas discharged from the first treatment chamber of the separation membrane module in the final stage is 80 mol% or more. Is preferable.
  • the combustion system according to the present invention is a combustion system including the CO 2 separation device of the second feature and the combustion device, and the first stage of the separation membrane module in the final stage of the CO 2 separation device.
  • the non-permeated gas discharged from the processing chamber is supplied to the combustion device as a fuel gas.
  • the steam supply unit of the CO 2 separation device generates steam by utilizing the waste heat from the combustion device.
  • water vapor is supplied to the impermeable gas discharged from the first treatment chamber of each separation membrane module other than the final stage, so that the separation membrane modules of the second and subsequent stages are supplied.
  • the decrease in CO 2 permeance accompanying the decrease in relative humidity is suppressed, and it becomes possible to maintain a desired CO 2 permeance.
  • high CO 2 permeance can be realized in all the separation membrane modules connected in series, and high selective permeability can be obtained as the separation membrane module sequence.
  • FIG. 1 Schematic sectional view schematically showing a basic configuration example of a separation membrane module used in the CO 2 separation apparatus according to the present invention.
  • FIG. 1 Schematic cross-sectional view schematically showing a basic configuration example of the CO 2 separation device according to the present invention.
  • the figure which shows the connection structure of the separation membrane module in each separation apparatus of the comparative example 4-7 Schematic configuration diagram schematically showing the main configuration of the combustion system according to the present invention.
  • FIG. 1 schematically shows a basic configuration example of the separation membrane module 2 used in the separation device 1.
  • FIG. 2 schematically shows a basic configuration example of the separation device 1.
  • the arrows in FIGS. 1 and 2 show the flow path and direction in which the gas flows in a simplified manner.
  • the dimensional ratio of each component shown in the schematic cross-sectional views of FIGS. 1 and 2 does not always match the actual dimensional ratio.
  • the configuration diagram of the main part of the combustion system described in the second embodiment described later Further, in each schematic cross-sectional view and the main part configuration diagram, the same components may be designated by the same reference numerals, and the description thereof may be omitted.
  • the separation membrane module 2 is a space in which a flat membrane-like CO 2 separation membrane 3 is housed in a housing 4 and surrounded by an inner wall of the housing 4 and a supply side surface of the CO 2 separation membrane 3.
  • the first treatment chamber 5 is formed
  • the second treatment chamber 6 is formed by the space surrounded by the inner wall of the housing 4 and the permeation side surface of the CO 2 separation membrane 3. That is, the first treatment chamber 5 and the second treatment chamber 6 are separated by the CO 2 separation membrane 3. Therefore, the housing 4 is a housing constituting the first processing chamber 5 and the second processing chamber 6.
  • the housing 4 is made of, for example, stainless steel, and although not shown, a fluororubber gasket is used as a sealing material between the outer peripheral end of the CO 2 separation membrane 3 and the inner wall of the housing 4 as an example.
  • the CO 2 separation membrane 3 is fixed in the housing 4.
  • the method for fixing and sealing the CO 2 separation membrane 3 is not limited to the above method. Further, the specific structure for fixing the CO 2 separation membrane 3 in the housing 4 differs depending on the shape of the CO 2 separation membrane 3 and the accommodation form in the housing 4, and therefore, in the present invention. Since there is no such thing, a detailed explanation will be omitted.
  • a first discharge port 8 is provided to discharge the non-permeated gas EG remaining in the first treatment chamber 5 from the first treatment chamber 5 to the outside without permeating the third.
  • the opening positions of the first inlet 7 and the first outlet 8 shown in FIG. 1 are exemplary, and the impermeable gas EG is constant along the supply side surface of the CO 2 separation membrane 3 in the first treatment chamber 5. As long as it flows in the direction, it can be appropriately changed according to the shape of the first processing chamber 5.
  • the second treatment chamber 6 is provided with a second discharge port 9 for discharging the permeated gas PG containing CO 2 that has permeated the CO 2 separation membrane 3 from the second treatment chamber 6 to the outside.
  • the second discharge port 9 is provided on the same side as the opening position of the first discharge port 8 on the opposite wall surface of the second processing chamber 6. That is, the direction in which the permeated gas PG flows along the permeation side surface of the CO 2 separation membrane 3 in the second treatment chamber 6 is along the supply side surface of the non-permeate gas EG CO 2 separation membrane 3 in the first treatment chamber 5. It is set in the same direction as the flow direction.
  • the opening position of the second discharge port 9 shown in FIG. 1 is an example, and corresponds to the shape of the second processing chamber 6 as long as the flow directions of the permeated gas PG and the non-permeated gas EG are “parallel flow”. Can be changed as appropriate.
  • the second processing chamber 6 is not provided with an inlet for feeding sweep gas or the like from the outside into the second processing chamber 6.
  • the CO 2 separation membrane 3 has a laminated structure in which a separation functional layer is supported on a hydrophilic porous membrane.
  • the separation functional layer is a layer for selectively permeating CO 2 , and in the present embodiment, as an example, a CO 2 carrier which is a compound that selectively reacts with CO 2 in a gel layer of a hydrophilic polymer. And functions as a facilitating transport membrane.
  • the hydrophilic porous film is a base material for applying a cast solution consisting of an aqueous solution containing a hydrophilic polymer in a step of forming a gel layer of a separation functional layer, and is obtained by gelling the hydrophilic polymer in the cast solution. It functions as a support film that supports the gel layer.
  • the process of forming the gel layer of the separation functional layer is disclosed in many patent documents and non-patent documents, and detailed description thereof will be omitted.
  • a hydrophobic porous membrane is laminated on the exposed surface to form a first protective film. good. Further, in order to protect the exposed surface on the opposite side of the separation functional layer support surface of the hydrophilic porous film, a hydrophobic porous film is laminated on the exposed surface to form a second protective film as a four-layer structure. Is also good.
  • hydrophilic polymer constituting the separation functional layer polyvinyl alcohol-polyacrylic acid (PVA / PAA) salt copolymer, polyvinyl alcohol, polyacrylic acid, chitosan, polyvinylamine, polyallylamine, polyvinylpyrrolidone and the like can be used.
  • PVA / PAA polyvinyl alcohol-polyacrylic acid
  • a hydrophilic polymer containing polyacrylic acid as a main component is preferably used.
  • the gel layer of the hydrophilic polymer may be a hydrogel. Hydrogel is a three-dimensional network structure formed by cross-linking a hydrophilic polymer, and often has a property of swelling by absorbing water.
  • the hydrophilic polymer is a PVA / PAA salt copolymer or polyvinyl alcohol
  • the degree of cross-linking of the hydrogel can be adjusted by adding a cross-linking agent such as a dialdehyde compound such as glutaraldehyde or an aldehyde compound such as formaldehyde. can.
  • a cross-linking agent such as a dialdehyde compound such as glutaraldehyde or an aldehyde compound such as formaldehyde.
  • the PVA / PAA salt copolymer may be referred to as a PVA / PAA copolymer.
  • carbonates of alkali metals such as cesium carbonate (Cs 2 CO 3 ) and rubidium carbonate (Rb 2 CO 3 ), bicarbonates, hydroxides, or glycine, Amino acids such as 2,3-diaminopropionate (DAPA), alanine, arginine, asparagine, serine, ornithine, creatine, threonine, sarcosin, and 2-aminobutyric acid are preferably used.
  • DAPA 2,3-diaminopropionate
  • the alkali may be any one having a strong basicity capable of depriving protonated NH 3+ of protons and converting it into NH 2 , and hydroxides or carbonates of alkali metal elements can be preferably used.
  • a CO dihydration reaction catalyst may be added to the gel layer of the hydrophilic polymer.
  • an oxoacid compound is preferably used as the CO dihydration reaction catalyst.
  • the CO dihydration reaction catalyst uses an oxo acid compound of at least one element selected from Group 6 elements, Group 14 elements, Group 15 elements, and Group 16 elements, and particularly.
  • a terrelic acid compound, a selenic acid compound, a arsenic acid compound, an orthosilicic acid compound, or a molybdic acid compound is used.
  • hydrophilic porous membrane polycarbonate (PC), polycellulose ester, polyetheretherketone (PEEK), a membrane obtained by hydrophilizing a hydrophobic porous membrane described later, and the like are preferably used.
  • porosity (porosity) of the hydrophilic porous membrane is preferably 55% or more, and the pore diameter of the hydrophilic porous membrane 11 is preferably in the range of 0.1 to 1 ⁇ m, preferably 0.1 to 1. It is more preferably in the range of 0.5 ⁇ m.
  • hydrophilic means that the contact angle with water at 25 ° C is less than 90 °.
  • the contact angle of the hydrophilic porous membrane is preferably 45 ° or less.
  • the hydrophobic porous film includes polytetrafluoroethylene (PTFE), polyethersulfone (PES), polypropylene (PP), polyethylene (PE), polyacrylonitrile (PAN), polysulfone (PS), polyethersulfone (PES), and polyimide. (PI), polyvinylidene fluoride (PVDF), etc. are preferably used. Further, the porosity (porosity) of the hydrophobic porous membrane is preferably 55% or more, and the pore diameter of the hydrophobic porous membrane is preferably in the range of 0.1 to 1 ⁇ m, and 0.1 to 0. It is more preferably in the range of .5 ⁇ m.
  • hydrophobic porous membrane means that the contact angle with water at 25 ° C is 90 ° or more.
  • the contact angle of the hydrophobic porous membrane is preferably 95 ° or more, more preferably 100 ° or more, still more preferably 105 ° or more.
  • the separation device 1 is configured to include a separation membrane module row in which a plurality of stages of the separation membrane module 2 (m stage: m is an integer of 2 or more) are connected in series, and a steam supply unit 11.
  • the plurality of stages of the separation membrane module 2 are the first stage, the second stage, ..., The mth stage (final stage) in order from the beginning along the flow direction of the mixed gas FG and the impermeable gas EG. Call.
  • the first inlet 7 of each separation membrane module 2 in the second and subsequent stages is connected to the first discharge port 8 of the separation membrane module 2 in the previous stage directly or via a connecting pipe.
  • the connecting portion 10 is configured with respect to the first discharge port 8 of the separation membrane module 2 in the previous stage. Except for the separation membrane module 2 in the final stage (mth stage), the connecting portion 10 is configured in the first discharge port 8 of each separation membrane module 2 in the first stage to the (m-1) stage. Since the number of connecting portions is one less than the number of stages m of the separation membrane module 2, for convenience, the order from the beginning of each connecting portion corresponds to the order of each separation membrane module 2 located in front of the connecting portion.
  • the m second discharge ports 9 of the m-stage separation membrane module 2 are connected to each other, and the permeated gas PG discharged from each second discharge port 9 is summarized. It is supplied to a device (not shown) that recovers or reuses the permeated gas PG.
  • the permeated gas PG contains a large amount of carbon dioxide and can be recovered and reused for various industrial uses. When the permeated gas PG is not recovered or reused and is released to the atmosphere, each second discharge port 9 may be left open.
  • steam ( H2O ) is supplied from the steam supply unit 11 to the connecting portion 10 of each separation membrane module 2 from the first stage to the (m-1) stage.
  • the impermeable gas EG discharged from the first discharge port 8 is the water vapor (H 2 O) supplied to the connecting portion 10.
  • it is supplied as a mixed gas FG into the first processing chamber 5 of the separation membrane module 2 in the next stage.
  • the amount of water vapor supplied to the connecting portion 10 of each stage is the amount required for the relative humidity of the non-permeated gas EG discharged to each connecting portion 10 to increase by 20% or more due to the supplied water vapor.
  • the relative humidity of the impermeable gas EG (mixed gas FG supplied to the separation membrane module 2 in the next stage) after increasing by 20% or more is preferably 50% or more and less than 100%, and further, the first stage. It is more preferable that the relative humidity of the mixed gas FG supplied to the separation membrane module 2 is equal to or substantially equal to (for example, within ⁇ 5%).
  • the relative humidity after the increase reaches 100%, or if the water vapor in the non-permeated gas EG condenses due to temperature fluctuations even if it is less than 100%, the relative humidity does not reach 100%.
  • the separation membrane module 2 of each stage in the separation membrane module 2 of each stage, until the mixed gas FG supplied into the first treatment chamber 5 passes through the first treatment chamber 5 and is discharged as a non-permeable gas EG.
  • the relative humidity drops by 20% or more.
  • the amount of water vapor supplied to the connecting portion 10 of each stage may be the same, or may be changed according to the degree of decrease in the relative humidity of the impermeable gas EG for each separation membrane module 2 of each stage.
  • the steam supply unit 11 is configured to heat water in the steam supply unit 11 to generate steam and distribute it to the connecting unit 10 of each stage, or collect steam from the outside into the steam supply unit 11. Two types of configurations are assumed, in which the components are distributed to the connecting portion 10 of each stage. Further, the steam supply unit 11 may be realized by combining two types of configurations. For example, as the latter configuration for collecting water vapor from the outside, the water vapor contained in the impermeable gas EG discharged from the separation membrane module 2 in the final stage (mth stage) is, for example, a perfluoro-based membrane (or perfluoro).
  • a water vapor removing unit that separates water vapor as it is by a known membrane separation method using a water vapor permeation film such as (sulfonic acid-based film) is provided, and the water vapor separated by the water vapor removing unit is collected in the water vapor supply unit 11.
  • the water vapor contained in the permeated gas PG discharged from the separation membrane module 2 of each stage is separated as water vapor by the water vapor removing unit of the above-mentioned membrane separation method and collected in the water vapor supply unit 11.
  • a configuration in which both are combined is assumed.
  • the relative humidity of the mixed gas FG supplied into the first treatment chamber 5 of the separation membrane module 2 in the second and subsequent stages is set to the mixed gas. It is possible to maintain the temperature above a predetermined value without lowering the temperature of the FG. As a result, in the separation membrane module 2 in the second and subsequent stages, it is possible to suppress the decrease in CO 2 permeance due to the decrease in relative humidity and maintain the desired CO 2 permeance. Therefore, the steam supply unit 11 of the separation device 1 distributes water vapor to the connection unit 10 of each stage, so that the separation membrane modules 2 are connected in series in a plurality of stages and used. The problem that the permeation rate of CO 2 is lowered in the separation membrane module is solved.
  • the mixed gas FG supplied from the first inlet 7 of the first-stage separation membrane module 2 into the first treatment chamber 5 is a specific gas that does not react with the CO 2 carrier contained in the separation functional layer of the CO 2 separation membrane 3. It is a mixed gas containing CO 2 and water vapor (H 2 O).
  • the specific gas is assumed to be H 2 , CH 4 , N 2 , O 2 , CO, etc., which do not react with CO 2 carriers in the separation functional layer and permeate only by the dissolution / diffusion mechanism.
  • a part of each gas component in the mixed gas FG remains in the first treatment chamber 5 without permeating the CO 2 separation membrane 3, so that the impermeable gas EG is also mixed.
  • the distribution ratio of each gas component is different from that of gas FG, it is a mixed gas containing a specific gas, CO 2 and water vapor (H 2 O).
  • the gas permeance of the specific gas permeating through the separation function layer of the CO 2 separation membrane 3 is about 100 times to several. An extremely high CO 2 permeance of about 1000 times can be realized, and high selective permeability is maintained.
  • the relative humidity of the mixed gas FG supplied from the first inlet 7 of the first-stage separation membrane module 2 into the first treatment chamber 5 is the CO 2 of the first-stage separation membrane module 2.
  • the desired CO 2 permit could be realized with a given CO 2 partial pressure difference.
  • the mixed gas FG supplied from the steam supply unit 11 to the separation membrane module 2 in the first stage is concerned.
  • a predetermined value for example, set within the range of 50% to 80%, 70% as an example
  • CO 2 in the mixed gas FG supplied into the first treatment chamber 5 selectively permeates the CO 2 separation membrane 3 with respect to the specific gas, thereby mixing. It is gradually separated from the gas FG. Then, each time the impermeable gas EG is discharged from the first treatment chamber 5 of each separation membrane module 2, the CO 2 concentration on the dry base in the impermeable gas EG gradually decreases, and conversely, the specific gas Concentration increases in stages.
  • a pipe for supplying the mixed gas FG into the first processing chamber 5 is connected to the first inlet 7 of the first-stage separation membrane module 2 and finally.
  • a pipe for discharging the impermeable gas EG from the first treatment chamber 5 to the outside is connected to the first discharge port 8 of the separation membrane module 2 of each stage, and the second discharge port 9 of the separation membrane module 2 of each stage is connected. Is connected to a pipe for discharging the permeated gas PG from the second processing chamber 6 to the outside.
  • each of the above pipes has a device for mixing multiple gas types, a device for adjusting or measuring the gas flow rate, a device for adjusting the gas supply pressure, and a gas back pressure.
  • a device for adding water vapor to the gas, a device for removing water in the gas, and the like are provided as necessary. The same applies to the configuration diagram of the main part of the combustion system described in the second embodiment described later.
  • FIG. 3 shows four types of interconnected structures of the separation membrane modules 2 in each of the separation devices of Example 1 and Comparative Examples 1 to 3.
  • FIG. 4 shows four types of interconnected structures of the separation membrane modules 2 in each of the separation devices of Comparative Examples 4 to 7. In each of the connecting structures shown in FIGS. 3 and 4, two separation membrane modules 2 are used.
  • the m-stage separation membrane module 2 of the separation device 1 shown in FIG. 2 is configured with a minimum number of two stages.
  • the connection structure of Example 1 is referred to as "series parallel flow intermediate humidification" for convenience.
  • Comparative Example 1 is a comparative example in which steam is not supplied to the connecting portion 10 carried out in Example 1.
  • the connected structure of Comparative Example 1 is referred to as "series parallel flow" for convenience.
  • Comparative Example 2 is a comparative example in which the temperature of the impermeable gas EG flowing through the connecting portion 10 is cooled by 10 ° C. instead of supplying water vapor to the connecting portion 10 carried out in the first embodiment.
  • the connection structure of Comparative Example 2 is referred to as "series parallel flow intermediate cooling" for convenience.
  • Comparative Example 3 is a comparative example in which water vapor is not supplied to the connecting portion 10 carried out in Example 1, and the flow directions of the permeated gas PG and the non-permeated gas EG in each separation membrane module 2 are opposite directions ( (Direct flow). Further, the permeated gas PG discharged from the second processing chamber 6 of the first stage is supplied to the second processing chamber 6 of the second stage.
  • the connected structure of Comparative Example 3 is referred to as "series countercurrent" for convenience.
  • Comparative Example 4 is a comparative example in which steam is not supplied to the connecting portion 10 carried out in Example 1, and steam is supplied as a sweep gas SG to the second treatment chamber 6 of the first stage, and the first stage is used.
  • the mixed gas MG of the permeated gas PG and the sweep gas SG discharged from the second processing chamber 6 of the eye is supplied to the second processing chamber 6 of the second stage.
  • the connection structure of Comparative Example 4 is referred to as a "series parallel flow connection sweep" for convenience.
  • Comparative Example 5 is a comparative example in which water vapor is not supplied to the connecting portion 10 carried out in Example 1, and water vapor is supplied as sweep gas SG to each of the second treatment chambers 6 of the first stage and the second stage. It is supplied separately. From the second treatment chamber 6 of each stage, the mixed gas MG of the permeated gas PG and the sweep gas SG is discharged to the outside.
  • the connected structure of Comparative Example 5 is referred to as "series parallel flow independent sweep" for convenience.
  • Comparative Example 6 is a comparative example in which two separation membrane modules 2 connected in series in Comparative Example 1 are separated and arranged in parallel.
  • the connected structure of Comparative Example 6 is referred to as "parallel parallel flow" for convenience.
  • Comparative Example 7 is a comparative example in which the flow directions of the permeated gas PG and the non-permeated gas EG in each separation membrane module 2 are opposite (countercurrent) to Comparative Example 6.
  • the connected structure of Comparative Example 7 is referred to as "parallel countercurrent" for convenience.
  • the mixed gas FG supplied to the separation membrane module 2 of the first stage is a mixed gas containing methane (CH 4 ), CO 2 and water vapor (H 2 O) in which the specific gas is methane (CH 4 ), and is dry.
  • the relative humidity RHFin (initial value) and the temperature T of the mixed gas FG are 80% and 110 ° C.
  • the effective membrane area of the CO 2 separation membrane 3 is 10 m 2 / module.
  • the pressure PF (absolute pressure) in the first processing chamber 5 and the pressure PS (absolute pressure) in the second processing chamber 6 of each separation membrane module 2 are 750 kPa and 101.3 kPa (atmospheric pressure). The pressure loss between the separation membrane modules 2 was ignored.
  • the supply gas flow rate of the mixed gas FG supplied to the separation membrane module 2 is F (dryNm 3 / h), and in Comparative Examples 6 and 7, the gas flow rate of the mixed gas FG supplied to the two separation membrane modules 2 is F /. 2 (the total gas flow rate is F).
  • the water vapor flow rate in the mixed gas FG supplied to the separation membrane module 2 in the first stage of Examples 1 and Comparative Examples 1 to 7 is LF (kg / h), and the water vapor flow rate is supplied to the connecting portion 10 of Example 1.
  • the steam flow rate supplied as the sweep gas SG of Comparative Examples 4 and 5 is LS (kg / h).
  • the water vapor flow rate LM is given as the water vapor flow rate required to return the relative humidity of the impermeable gas EG discharged from the first-stage separation membrane module 2 to the relative humidity RHFin (80%).
  • the steam flow rate LS was set to be the same as the steam flow rate LM.
  • Example 1 simulations were performed for Example 1 and Comparative Examples 1 to 7 under the above conditions, and the supply gas flow rate F (dryNm 3 / h) and the total steam flow rate L when the recovered methane concentration reached 80 mol%. / The supply gas flow rate F (kg / Nm 3 ) was determined.
  • the simulation results are summarized in Table 1 below.
  • this separation device 1 of the "series parallel flow intermediate humidification" type means that the yield of purified methane gas having a given recovered methane concentration per unit time is large, and the production efficiency of purified methane gas is high. This indicates that the CO 2 separation performance of the separation device 1 with respect to the mixed gas FG is high.
  • the "series parallel flow intermediate humidification" type main separation device 1 has a large yield per unit time of purified methane gas having a predetermined recovered methane concentration even when compared with the parallel type connected structure, and has a production capacity of purified methane gas. Means that is high. This indicates that the CO 2 separation performance of the separation device 1 with respect to the mixed gas FG is high.
  • FIG. 5 schematically shows the main configuration of the combustion system 20.
  • the combustion system 20 includes the separation device 1 and the combustion device 21.
  • the mixed gas FG supplied into the first treatment chamber 5 of the separation membrane module 2 of the first stage of the separation device 1 includes a component derived from biogas produced by methane fermentation of an organic substance. It is assumed that the mixed gas is a mixed gas containing methane (CH 4 ), CO 2 and water vapor (H 2 O).
  • the mixed gas FG supplied to the separation membrane module 2 in the first stage is referred to as “raw material gas FG1”, and the mixed gas FG supplied to the first processing chamber 5 of the separation membrane module 2 in the second and subsequent stages is referred to. To distinguish from.
  • the separation device 1 can remove CO 2 from the raw material gas FG 1 and supply the impermeable gas EG containing high-purity methane to the combustion device 21 from the separation membrane module 2 in the final stage.
  • the methane concentration (recovered methane concentration) of the impermeable gas EG discharged from the separation membrane module 2 in the final stage is determined by adjusting the gas supply flow rate and gas supply pressure of the raw material gas FG1 and adjusting the raw material gas FG1 and the raw material gas FG1 by the steam supply unit 11. By adjusting various parameters such as adjustment of the relative humidity of the non-permeated gas EG in each connecting portion 10, it is possible to control the concentration to be the desired high concentration.
  • the combustion device 21 is, for example, a gas engine, a gas turbine, or the like, and converts the thermal energy generated by the combustion reaction of high-purity methane contained in the supplied impermeable gas EG into energy such as kinetic energy and electric power.
  • the combustion device 21 is not limited to a specific combustion device as long as it is compatible with the combustion of methane.
  • impurities such as hydrogen sulfide and siloxane are removed in advance by using an existing desulfurization device (not shown), an activated carbon adsorption type siloxane removal device, or the like.
  • an existing desulfurization device not shown
  • an activated carbon adsorption type siloxane removal device or the like.
  • the desulfurization apparatus a wet desulfurization method using an absorbent liquid or an adsorption desulfurization method using a sulfur adsorbent such as zinc oxide or iron oxide can be used.
  • sulfur a copper-zinc-based ultra-high-order desulfurization catalyst is used, sulfur can be completely removed to the ppb level or lower. It is preferable to use an ultra-high-order desulfurization catalyst because it may be affected by hydrogen sulfide depending on the type and concentration of the CO 2 carrier used in the separation membrane module 2 of the separation device 1.
  • the steam supply unit 11 provided as a part of the separation device 1 is mainly for supplying steam to the connecting unit 10, but the steam in the raw material gas FG1.
  • a predetermined value for example, set within the range of 50% to 80%, 70% as an example
  • steam is supplied from the steam supply unit 11 to the raw material gas FG1. It is preferable to supply and control the relative humidity to be equal to or higher than the above-mentioned predetermined value.
  • the steam supply path is shown by a dotted line.
  • a hygrometer (not shown) is arranged on the flow path of the raw material gas FG1, and the water vapor supply unit 11 supplies water vapor to the raw material gas FG1 based on the measured value of the hygrometer.
  • the non-permeable gas supplied to the combustion device 21 is provided in the gas flow path between the first discharge port 8 of the separation membrane module 2 of the first stage of the separation device 1 and the gas supply port of the combustion device 21.
  • a water vapor removing unit 22 for removing water vapor contained in the EG is interposed.
  • the permeation is permeated.
  • Another steam removing section may be provided in the gas flow path of the gas PG to recover the steam in the permeated gas PG and reuse it as the steam supplied to the connecting section 10 in the steam supply section 11.
  • the water vapor removing unit 22 and the water vapor removing unit provided in the gas flow path of the permeated gas PG recover the water vapor in the non-permeated gas EG and the permeated gas PG as water instead of recovering as water vapor.
  • the recovered water may be heated to generate steam and used in the steam supply unit 11.
  • high-temperature exhaust gas generated by combustion of methane in the combustion device 21 can be used as a heat source for heating.
  • the combustion system 20 described in the present embodiment for example, when a gas engine is used as the combustion device 21, a biogas having a large fluctuation in methane concentration is used as the fuel supplied to the combustion system 20. Even so, since high-purity methane gas with suppressed fluctuations in methane concentration can be supplied to the gas engine, stable output can be obtained without the need for complicated engine adjustment work, resulting in miniaturization and high output. Can be expected.
  • each separation membrane module 2 is as shown in FIG.
  • One separation membrane module 2 is assumed.
  • the separation membrane module 2 in each stage may be configured by connecting two or more separation membrane modules 2 in parallel, whereby the effective membrane area per stage of the separation membrane module 2 is increased.
  • the processing capacity of the separation device 1 may be increased.
  • the first inlets 7 of the two or more separation membrane modules 2 are connected to each other to form one first inlet / outlet 7, and the first outlets 8 of the two or more separation membrane modules 2 are also connected to each other. It is connected to each other to form one first discharge port 8, and the two or more separation membrane modules 2 function as one separation membrane module 2.
  • a flat plate type in which the flat membrane-like CO 2 separation membrane 3 is used as it is.
  • one or more CO 2 separation membranes 3 having a cylindrical type having a cylindrical two-layer to four-layer structure and a flat membrane-like structure having a two -layer to four-layer structure are spirally formed.
  • the spiral type which has a shape of being wound multiple times, or the pleated type, which has a flat membrane-like one or a plurality of CO 2 separation membranes 3 having a two-layer to four-layer structure folded in a bellows shape. It may be in the shape of.
  • the CO 2 separation device and the CO 2 separation method according to the present invention use a plurality of stages of separation membrane modules that selectively separate carbon dioxide in series, and selectively select carbon dioxide from a mixed gas containing carbon dioxide. It can be used to separate.
  • CO 2 separation device 2 Separation membrane module 3: CO 2 separation membrane 4: Housing 5: 1st treatment chamber 6: 2nd treatment chamber 7: 1st inlet 8: 1st discharge port 9: 2nd discharge Outlet 10: Connecting part 11: Steam supply part 20: Combustion system 21: Combustion device 22: Steam removal part FG: Mixed gas FG1: Raw material gas EG: Non-permeated gas PG: Permeated gas SG: Sweep gas MG: Permeated gas and sweep Mixed gas of gas

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Water Supply & Treatment (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

La présente invention concerne un procédé et un dispositif de séparation de CO2 qui utilisent une pluralité d'étages de modules à membrane de séparation connectés en série, une diminution de la perméance de CO2 dans un module à membrane de séparation aval étant supprimée. Les modules à membrane de séparation (2) sont chacun pourvus d'une membrane de séparation (3) de CO2 qui comprend un vecteur de CO2, une première chambre de traitement (5) et une seconde chambre de traitement (6). Dans chaque module à membrane de séparation (2), un gaz mixte FG comprenant un gaz spécifique, du dioxyde de carbone et de la vapeur d'eau est introduit dans la première chambre de traitement (5) à partir d'un côté d'extrémité de la première chambre de traitement (5), le dioxyde de carbone dans le gaz mixte FG traverse la membrane de séparation de CO2 vers le côté de la seconde chambre de traitement (6) et est séparé, le gaz non perméable EG qui ne traverse pas la membrane de séparation (3) de CO2 et reste dans la première chambre de traitement (5), est évacué de l'autre côté d'extrémité de la première chambre de traitement (5) et le gaz perméable PG qui a traversé la membrane de séparation (3) de CO2 est évacué vers l'extérieur à partir de la seconde chambre de traitement (6). Dans chaque module à membrane de séparation (2) autre que le module à membrane de séparation (2) le plus en aval, de la vapeur d'eau est ajoutée au gaz non perméable EG évacué de la première chambre de traitement (5) et ensuite le gaz non perméable EG est fourni sous forme de gaz mixte FG à la première chambre de traitement (5) du module à membrane de séparation aval (2).
PCT/JP2021/021826 2020-08-25 2021-06-09 Procédé de séparation de co2, dispositif de séparation de co2 et système de combustion WO2022044481A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11200817A (ja) * 1998-01-05 1999-07-27 Central Res Inst Of Electric Power Ind 水素分離型火力発電システム
JP2009242773A (ja) * 2008-03-14 2009-10-22 Air Water Inc メタンガス濃縮装置および方法ならびに燃料ガスの製造装置および方法
JP2014200767A (ja) * 2013-04-09 2014-10-27 住友化学株式会社 ガス分離装置及びそれを用いた酸性ガスの分離方法
JP2017148736A (ja) * 2016-02-24 2017-08-31 次世代型膜モジュール技術研究組合 二酸化炭素の回収方法及びガス分離膜モジュール

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11200817A (ja) * 1998-01-05 1999-07-27 Central Res Inst Of Electric Power Ind 水素分離型火力発電システム
JP2009242773A (ja) * 2008-03-14 2009-10-22 Air Water Inc メタンガス濃縮装置および方法ならびに燃料ガスの製造装置および方法
JP2014200767A (ja) * 2013-04-09 2014-10-27 住友化学株式会社 ガス分離装置及びそれを用いた酸性ガスの分離方法
JP2017148736A (ja) * 2016-02-24 2017-08-31 次世代型膜モジュール技術研究組合 二酸化炭素の回収方法及びガス分離膜モジュール

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