WO2021079609A1 - Membrane de transport facilitée de co2, son procédé de production et procédé et dispositif de séparation de co2 - Google Patents

Membrane de transport facilitée de co2, son procédé de production et procédé et dispositif de séparation de co2 Download PDF

Info

Publication number
WO2021079609A1
WO2021079609A1 PCT/JP2020/032069 JP2020032069W WO2021079609A1 WO 2021079609 A1 WO2021079609 A1 WO 2021079609A1 JP 2020032069 W JP2020032069 W JP 2020032069W WO 2021079609 A1 WO2021079609 A1 WO 2021079609A1
Authority
WO
WIPO (PCT)
Prior art keywords
membrane
film
gel
hygroscopic agent
transport
Prior art date
Application number
PCT/JP2020/032069
Other languages
English (en)
Japanese (ja)
Inventor
岡田　治
和美 秋山
保 野々内
Original Assignee
株式会社ルネッサンス・エナジー・リサーチ
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 株式会社ルネッサンス・エナジー・リサーチ filed Critical 株式会社ルネッサンス・エナジー・リサーチ
Priority to JP2021554109A priority Critical patent/JP7161253B2/ja
Publication of WO2021079609A1 publication Critical patent/WO2021079609A1/fr

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
    • B01D71/60—Polyamines
    • 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
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/10—Supported membranes; Membrane supports
    • B01D69/107—Organic support material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B01D69/1216—Three or more layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B01D71/0213—Silicon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/08—Polysaccharides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/38—Polyalkenylalcohols; Polyalkenylesters; Polyalkenylethers; Polyalkenylaldehydes; Polyalkenylketones; Polyalkenylacetals; Polyalkenylketals
    • B01D71/381—Polyvinylalcohol
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
    • B01D71/401—Polymers based on the polymerisation of acrylic acid, e.g. polyacrylate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/44—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of groups B01D71/26-B01D71/42
    • B01D71/441—Polyvinylpyrrolidone
    • 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
    • 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 relates to a CO 2 promoted transport membrane used for separating carbon dioxide (CO 2 ), and more particularly to a CO 2 promoted transport membrane that separates carbon dioxide produced as a by-product in a hydrogen production process or the like at a high selective ratio with respect to hydrogen. also relates to processes for the manufacture of the CO 2 -facilitated transport membrane, to CO 2 separation method and device using the CO 2 -facilitated transport membrane.
  • Chemical absorption method used in the decarboxylation process large plants requires regenerator giant CO 2 absorption tower and CO 2 absorbing solution in the separation of CO 2 in the regeneration step the CO 2 absorbing solution, since it requires a large amount of steam to remove CO 2 from the heated absorption liquid for re-use liquid imbibed with CO 2, wasteful consumption of energy doing.
  • CCS Carbon dioxide Capture and Storage
  • the separation is performed by the speed difference of the gas passing through the membrane using the pressure difference as the driving energy, and the pressure of the separated gas can be used as energy.
  • it is expected as an energy-saving process because it does not involve phase change.
  • Gas separation membranes are roughly classified into organic membranes and inorganic membranes depending on the membrane material.
  • Organic films have the advantages of being cheaper and more moldable than inorganic films.
  • the organic membrane used for gas separation is generally a polymer membrane prepared by the phase conversion method, and the mechanism of separation is the solubility of gas in the membrane material and the diffusion rate of gas in the membrane. It is based on a dissolution / diffusion mechanism that separates gases due to differences.
  • the dissolution / diffusion mechanism is based on the idea that the gas first dissolves on the surface of the polymer membrane, and the dissolved molecules diffuse in the polymer chain gaps in the polymer membrane.
  • the permeability coefficient P A of gas components A, solubility coefficient S A, when the diffusion coefficient is D A, relational expression P A S A ⁇ D A is satisfied.
  • S A / S B solubility selectivity, D A / D B is called the diffusion selectivity.
  • a permeation membrane called a facilitative transport membrane which uses a substance called a "carrier” that selectively and reversibly reacts with CO 2 and selectively permeates gas by a facilitative transport mechanism in addition to a dissolution / diffusion mechanism.
  • the accelerated transport mechanism has a structure in which a carrier that selectively reacts with CO 2 is contained in the membrane.
  • CO 2 in addition to physical permeation by the dissolution / diffusion mechanism, CO 2 also permeates as a reaction product with carriers, so that the permeation rate is promoted.
  • Patent Document 1 by using a specific alkali metal salt such as cesium carbonate or rubidium carbonate as a carrier, CO 2 permeance and CO 2 / H 2 selectivity that can be practically used under high temperature conditions of 100 ° C. or higher are provided.
  • a CO 2 promoted transport membrane has been proposed.
  • Carbon dioxide is promoted and transported even when there is little water in the membrane, but since its permeation rate is generally low, it is necessary to retain a large amount of water in the membrane in order to obtain a high permeation rate.
  • CO 2 permeance and CO 2 selective permeability for example, CO 2 / H 2 selectivity
  • an object of the present invention is to stably supply a CO 2 promoted transport membrane having improved CO 2 permeance and CO 2 selective permeability.
  • the present invention provides a CO 2 promoting transport membrane characterized by containing a CO 2 carrier and a particulate hygroscopic agent in a gel membrane of a hydrophilic polymer.
  • Carbon dioxide is promoted and transported even when there is little water in the membrane, but since its permeation rate is generally low, it is necessary to retain a large amount of water in the membrane in order to obtain a high permeation rate. Therefore, according to the CO 2 promoting transport membrane having the above characteristics, since the gel membrane contains a particulate hygroscopic agent, the water retention capacity of the gel membrane is improved, and the CO 2 permeance and the CO 2 selective permeability are improved. There is expected.
  • the hygroscopic agent is porous particles.
  • the hygroscopic performance is improved by increasing the specific surface area of the hygroscopic agent, and further improvement in CO 2 permeance and CO 2 selective permeability is expected.
  • the hygroscopic agent is dispersed in the gel membrane. As a result, uniform improvement is expected over the entire surface of the CO 2 promoted transport membrane having CO 2 permeance and CO 2 selective permeability.
  • the particle size of the hygroscopic agent is 75 ⁇ m or less. Since it is assumed that the thickness of the gel film of the CO 2 promoting transport film is as thin as about 200 ⁇ m, if the particle size exceeds 75 ⁇ m, the film performance may deteriorate due to defects penetrating the gel film.
  • the particle size is preferably suppressed to about 40% or less, more preferably about 35% or less, based on the thickness of the gel film.
  • the hygroscopic agent is a silicon compound.
  • Silica gel, zeolite and the like are assumed as silicon compounds that can be used as a hygroscopic agent.
  • the hydrophilic polymer is selected from polyvinyl alcohol-polyacrylate copolymer, polyvinyl alcohol, polyacrylic acid, chitosan, polyvinylamine, polyallylamine, and polyvinylpyrrolidone. It is preferably a polymer to be used.
  • those skilled in the art may refer to the polyvinyl alcohol-polyacrylate copolymer as a polyvinyl alcohol-polyacrylic acid copolymer.
  • the CO 2 carrier contains at least one of an alkali metal carbonate, an alkali metal bicarbonate, an alkali metal hydroxide, and an amino acid. It is preferable that the alkali metal is composed of cesium or rubidium. Further, as an amino acid that can be used as a CO 2 carrier, for example, glycine, 2,3-diaminopropionate (DAPA) and the like are assumed.
  • the gel membrane is a hydrogel.
  • Hydrogel is a three-dimensional network structure formed by cross-linking a hydrophilic polymer, and has the property of swelling by absorbing water.
  • the CO 2 promoting transport membrane having the above characteristics, by forming the gel membrane with a hydrogel having high water retention, the water retention capacity of the gel membrane is improved, and further improvement in CO 2 permeance and CO 2 selective permeability is expected. Will be done.
  • the gel membrane is supported on a hydrophilic porous membrane.
  • the strength of the CO 2 promoting transport membrane during use is improved.
  • the pressure of the CO 2 -facilitated transport membrane when applied to CO 2 permeable membrane reactor (CO 2 -facilitated transport membrane CO transformer having a), on both sides of the CO 2 -facilitated transport membrane (reactor internal and external) Sufficient film strength can be secured even if the difference is large (for example, 2 atm or more).
  • the porous membrane when the porous membrane is hydrophobic, it is possible to prevent the moisture in the gel membrane from invading the pores in the porous membrane at 100 ° C. or lower and lower the membrane performance, and the gel at 100 ° C. or higher. Since the same effect can be expected even when the water content in the membrane is low, the use of a hydrophobic porous membrane is recommended, but the reason why the porous membrane that supports the gel membrane is hydrophilic will be described later. As a result, a gel film with few defects can be stably produced, and high selective permeability to hydrogen can be maintained.
  • the CO 2 promoted transport film having the above characteristics is used to supply a mixed gas containing a predetermined main component gas and CO 2 to the CO 2 promoted transport film, and the CO 2 promoted transport from the mixed gas.
  • a CO 2 separation method characterized by separating the CO 2 that has permeated the membrane.
  • the present invention includes a CO 2 -facilitated transport membrane having the above characteristics, supplying a mixed gas containing a predetermined main component gas and CO 2 in the CO 2 -facilitated transport membrane, the CO 2 -facilitated transport membrane from the mixed gas
  • a CO 2 separation apparatus characterized by separating the CO 2 that has passed through the gas.
  • the present invention is a method for producing a CO 2 promoted transport film having the above-mentioned characteristics, wherein a step of preparing a sol solution composed of an aqueous solution containing the hydrophilic polymer, the CO 2 carrier, and the hygroscopic agent, and the above.
  • a method for producing a CO 2- promoted transport film which comprises a step of casting a sol solution into a hydrophilic porous film and then gelling to prepare the gel film.
  • the sol solution when the sol solution is cast on the hydrophilic porous membrane in the step of producing the gel membrane, the pores of the porous membrane are filled with the sol solution, and further. , The sol solution is applied to the surface of the porous membrane.
  • a gel film is produced by gelling this sol solution, the gel film is filled not only on the surface of the porous film but also in the pores, so that defects are less likely to occur and the success rate of gel film formation is increased. ..
  • the gel film in the pores has a large resistance to gas permeation.
  • the permeability is lower than that of the gel membrane on the surface of the porous membrane, and the gas permeance is lowered.
  • the cast solution is cast on the hydrophobic porous membrane, the inside of the pores of the porous membrane is not filled with the liquid, the cast solution is applied only to the surface of the porous membrane, and the pores are filled with gas.
  • the gas permence in the upper gel layer is expected to be higher than that of the hydrophilic porous membrane.
  • the gel film on the surface of the film is more likely to have minute defects, and the success rate of film formation is lowered.
  • H 2 has a much smaller molecular size than CO 2 , so H 2 is better than CO 2 at minute defects.
  • Permeance is significantly increased. Except for the defective part, the CO 2 permeance transmitted by the accelerated transport mechanism is much larger than the H 2 permeance transmitted by the physical dissolution and diffusion mechanism.
  • the hydrogen selectivity (CO 2 / H 2 ) when the hydrophobic porous membrane is used is lower than that when the hydrophilic porous membrane is used. Therefore, from the viewpoint of practical use, the stability and durability of the CO 2 promoted transport membrane are very important, and it is advantageous to use a hydrophilic porous membrane having high hydrogen selectivity (CO 2 / H 2). Become.
  • the hydrophilic polymer and the CO 2 carrier are added to pure water to which the hygroscopic agent has been added first, and the mixture is stirred. It is preferable to do so.
  • the process of preparing the sol solution by adding the hygroscopic agent to the pure water first, it is possible to adsorb the water molecules of the pure water to the hygroscopic agent without being affected by the CO 2 carriers added later. It is possible to increase the water retention of the gel film.
  • CO 2 promoted transport membrane having the above characteristics and the method for producing the same, a CO 2 promoted transport membrane having improved CO 2 permeance and CO 2 selective permeability (for example, CO 2 / H 2 selectivity) is stably supplied. be able to.
  • CO 2 and H 2 and the like can be obtained by using a CO 2 promoting transport film having high CO 2 selective permeability (for example, CO 2 / H 2 selectivity). It is possible to selectively separate CO 2 from a mixed gas containing the main component gas of the above with high efficiency.
  • FIG. 3 is a graph showing the film performance (CO 2 permeance, H 2 permeance, CO 2 / H 2 selectivity) of sample S1 of Example 1 and sample C1 of Comparative Example 1 shown in FIG.
  • FIG. 3 is a graph showing the CO 2 / H 2 selectivity of samples S2 to S6 of Example 1 and sample C2 of Comparative Example 1 shown in FIG.
  • FIG. 3 is a graph showing the CO 2 / H 2 selectivity of the samples G2 to G7 of Example 2 and the sample C2 of Comparative Example 1 shown in FIG.
  • the present inventor has by extensive studies, the gel film of occurrence of the reaction of CO 2 and CO 2 carrier shown in the above (Formula 1) containing CO 2 carrier of CO 2 facilitated transport membrane, free of particulate desiccant It was found that the CO 2 permeance was improved with respect to the H 2 permeance, and the CO 2 / H 2 selectivity was improved as compared with the conventional CO 2 promoting transport film containing no such hygroscopic agent. Then, based on the above new findings, the inventor of the present application has invented the CO 2 promoting transport membrane shown below, a method for producing the same, and a CO 2 separation method and apparatus.
  • This accelerated transport membrane contains a CO 2 carrier and a particulate hygroscopic agent in a gel membrane of a hydrophilic polymer containing water , and has high CO 2 permeation and CO 2 selective permeability (for example, CO 2 / H 2 selectivity).
  • a CO 2 facilitated transport membrane having a applicable a CO 2 -facilitated transport membrane to CO 2 permeable membrane reactor, and the like.
  • a hydrophilic porous membrane is adopted as a support membrane for supporting the gel membrane in order to stably realize high CO 2 selective permeability.
  • this accelerated transport film is, for example, a polyvinyl alcohol-polyacrylic acid (PVA / PAA) salt copolymer, polyvinyl alcohol, polyacrylic acid, chitosan as a hydrophilic polymer which is a film material of a gel film.
  • PVA / PAA polyvinyl alcohol-polyacrylic acid
  • DAPA 2,3-diaminopropionate
  • porous particles such as silica gel and graphite are used as the particulate hygroscopic agent.
  • the graphite surface is modified with a surfactant to reduce water repellency by the method described later.
  • the particulate hygroscopic agent used is one in which the particle size is classified to 75 ⁇ m or less by sieving.
  • the reason for classifying the particle size to 75 ⁇ m or less is that the film thickness of the gel film is assumed to be about 200 ⁇ m to 300 ⁇ m. Therefore, when the particle size exceeds 75 ⁇ m, a path penetrating the gel film via the hygroscopic agent is created. This is because there is a high possibility that it will be formed as a defect, and there is a concern that the film performance, particularly the CO 2 selective permeability, will be deteriorated.
  • this accelerated transport membrane is composed of a hydrophilic porous membrane 2 carrying a gel membrane 1 and a three-layer structure supported by a hydrophobic porous membrane 3, as schematically shown in FIG. ..
  • the hydrophilic porous membrane 2 supporting the gel film 1 may have a four-layer structure sandwiched between two hydrophobic porous membranes 3. Since the gel film 1 is supported by the hydrophilic porous film 2 and has a certain mechanical strength, it does not necessarily have to have a structure supported or sandwiched by the hydrophobic porous film 3. For example, the mechanical strength can be enhanced by forming the hydrophilic porous membrane 2 in a cylindrical shape. Therefore, the accelerated transport membrane is not necessarily limited to a flat plate.
  • the hydrophilic polymer is present in the gel film in the range of about 10 to 80% by weight, and the CO 2 carrier is about 20 to 90% by weight. It exists in the range of%.
  • the particulate hygroscopic agent is, for example, about 0.01 to 0.2% by weight, more preferably about 0.01 to 0.1% by weight, based on the total weight of the sol solution excluding the hygroscopic agent described later.
  • % Is present in the gel membrane.
  • about 0.12 to 2.4% by weight more preferably about 0.12 to 1.2% by weight is present.
  • weight of the hydrophilic polymer there are about 0.44 to 8.8% by weight, more preferably about 0.44 to 4.4% by weight.
  • the hydrophilic porous membrane preferably has heat resistance of 100 ° C. or higher, mechanical strength, and adhesion to the gel membrane, and further has a porosity (porosity) of 55% or higher and is fine.
  • the pore diameter is preferably in the range of 0.1 to 1 ⁇ m.
  • PTFE hydrophilic tetrafluoroethylene polymer
  • the hydrophobic porous membrane preferably has heat resistance of 100 ° C. or higher, mechanical strength, and adhesion to the gel membrane, and further has a porosity (porosity) of 55% or higher and is fine.
  • the pore diameter is preferably in the range of 0.1 to 1 ⁇ m.
  • PTFE non-hydrophilic ethylene tetrafluoroethylene polymer
  • a sol solution composed of an aqueous solution containing a PVA / PAA salt copolymer, a CO 2 carrier, and a particulate hygroscopic agent is prepared (step 1). More specifically, 50 g of pure water and a predetermined amount of hygroscopic agent are added to a container (for example, a weighing bottle) and stirred to adsorb water molecules of pure water to the hygroscopic agent, and then a PVA / PAA salt copolymer.
  • the amount of the hygroscopic agent added was adjusted within the range of 0.01 to 0.2% by weight with respect to the total weight of the sol solution excluding the hygroscopic agent.
  • the surface of graphite is surface-modified with a surfactant in advance to reduce water repellency in the following manner.
  • the surface modification treatment is carried out by adding graphite particles to a mixture of 30 g of pure water and 0.3 g of a surfactant and stirring with a stirrer for 24 hours.
  • the nonionic surfactant acetylenol E00 is used as the surfactant, but if it is possible to surface-modify graphite as the surfactant to reduce water repellency, the nonionic surfactant is used. It is not limited to the agent, and even a nonionic surfactant is not limited to acetylenol E00.
  • step 1 As a post-step of step 1, 0.125 g of water-soluble nylon may be added to the sol solution obtained in step 1 and stirred at 80 ° C. for 24 hours.
  • the sol solution obtained in step 1 or the post-step of step 1 is subjected to a hydrophilic PTFE porous membrane (for example, manufactured by Sumitomo Electric Fine Polymer, WPW-020-80, film thickness 80 ⁇ m, pore diameter 0.2 ⁇ m, void ratio).
  • a hydrophilic PTFE porous membrane for example, manufactured by Sumitomo Electric Fine Polymer, WPW-020-80, film thickness 80 ⁇ m, pore diameter 0.2 ⁇ m, void ratio.
  • hydrophobic PTFE porous membrane for example, manufactured by Sumitomo Electric Fine Polymer, Fluoropore FP010, film thickness 60 ⁇ m, pore diameter 0.1 ⁇ m, void ratio about 55%) Cast with an applicator on the surface of the PTFE porous membrane side (step 2).
  • the cast thickness of the samples of Examples and Comparative Examples described later is 500 ⁇ m.
  • the sol solution permeates into the pores in the hydrophilic PTFE porous membrane, but the permeation stops at the interface of the hydrophobic PTFE porous membrane, and the sol solution does not permeate to the opposite surface of the layered porous membrane. There is no sol solution on the side surface of the hydrophobic PTFE porous membrane of the layered porous membrane, which facilitates handling.
  • gelation means that a sol solution, which is a dispersion liquid of a polymer, is dried to form a solid state, and a gel film is a solid film produced by the gelation, and is a liquid film. Clearly distinguished.
  • the gel film is formed on the surface (cast surface) of the hydrophilic PTFE porous membrane in step 3. Since it is formed by filling the pores as well as being formed, defects (micro defects such as pinholes) are less likely to occur, and the success rate of gel film formation is increased.
  • step 3 it is desirable that the naturally dried PTFE porous membrane is further thermally crosslinked at a temperature of about 120 ° C. for about 2 hours. In the samples of Examples and Comparative Examples described later, thermal cross-linking is performed. By thermal cross-linking, the film thickness of the gel film becomes about 200 ⁇ m.
  • the hydrophilic porous membrane 2 carrying the gel film 1 is supported by the hydrophobic porous membrane 3, and this accelerated transport membrane has a three-layer structure.
  • the same hydrophobic PTFE porous membrane as the hydrophobic PTFE porous membrane of the layered porous membrane used in step 2 was overlaid on the gel layer side of the surface of the hydrophilic PTFE porous membrane obtained in step 3, and the gel film was formed.
  • the main accelerated transport membrane having a four-layer structure in which the hydrophilic porous membrane 2 carrying 1 is sandwiched between two hydrophobic porous membranes 3 may be obtained.
  • FIG. 1 the state in which the gel film 1 is filled in the pores of the hydrophilic PTFE porous film 2 is schematically shown linearly.
  • the samples S1 to S6 and G1 to G7 are produced through the steps 1 (including the post-step) to 3 of the above-mentioned manufacturing method, and the samples C1 to C2 have a hygroscopic agent in the sol solution in the step 1. It was prepared in the same manner as the samples S1 to S6 and G1 to G7 except that it was not added, and the sample C3 was subjected to a surface modification treatment with a surfactant on the graphite particles added in step 1. It is prepared in the same manner as the samples G1 to G7 except that the sample G1 to G7 is not used.
  • the amount of the PVA / PAA salt copolymer and cesium carbonate added is the same between the samples of Example 1, Example 2, Comparative Example 1, and Comparative Example 2, and the amount of the particulate hygroscopic agent is the same. Except for differences in the amount added or the presence or absence of surface modification treatment on graphite particles There is no difference in manufacturing conditions.
  • the addition amounts of the silica gel particles of the samples S1 to S6 of Example 1 were, in order, 0.08% by weight and 0.01% by weight with respect to the total weight of the sol solution excluding the hygroscopic agent. , 0.02% by weight, 0.05% by weight, 0.08% by weight, and 0.1% by weight.
  • the amount of the surface-modified graphite particles added to the samples G1 to G7 of Example 2 was, in order, 0.01% by weight based on the total weight of the sol solution excluding the hygroscopic agent. , 0.01% by weight, 0.04% by weight, 0.05% by weight, 0.08% by weight, 0.1% by weight, 0.2% by weight.
  • the amount of the particulate hygroscopic agents (silica gel particles, graphite particles) added to the samples C1 to C2 of Comparative Example 1 was 0, and the surface-modified untreated graphite of Sample C3 of Comparative Example 2 was added.
  • the amount of particles added is set to 0.01% by weight with respect to the total weight of the sol solution excluding the hygroscopic agent.
  • Each sample was used by fixing a fluororubber gasket as a sealing material between the supply side chamber and the permeation side chamber of the stainless steel flow-type gas permeation cell.
  • the experimental conditions are common to each sample, and the flow-type gas permeation cell is installed in a constant temperature bath (electric furnace), and the temperature in the cell is fixed at 160 ° C.
  • the relative humidity in the cell is 80%.
  • the supply-side gas supplied to the supply-side chamber is a mixed gas consisting of CO 2 , H 2 , and H 2 O (steam). Specifically, CO 2 and H 2 are supplied at a flow rate of 100 ml / min, respectively. was allowed to merge, it is produced by mixing and H 2 O (steam) by passing the bubbler (humidifier).
  • the supply side pressure is 445 kPa (G). In addition, (G) means gauge pressure.
  • the pressure in the permeation concubine is atmospheric pressure. The pressures in the supply side chamber and the permeation side chamber are adjusted by providing a back pressure regulator on the downstream side of the cooling trap in the middle of the exhaust gas discharge path.
  • the gas that has permeated the accelerated transport membrane of each sample is collected in a container after passing through a cooling trap from the permeation side chamber side, and is quantified by a gas chromatograph.
  • the amount of gas that has passed through the accelerated transport membrane of each sample is small, and in order to match the CO 2 concentration within the measurement range of the gas chromatograph, N 2 is used as a dilution gas in the container at a flow rate of 100 ml / min.
  • N 2 is used as a dilution gas in the container at a flow rate of 100 ml / min.
  • the permeance of CO 2 and H 2 [mol / (m 2 ⁇ s ⁇ kPa)] is calculated from the result quantified by the gas chromatograph and the flow rate of N 2 , and the CO 2 / H 2 selectivity is calculated from the ratio.
  • FIG. 4 (A) shows the CO 2 permeance and the H 2 permeance of the samples S1 and C1 as a graph
  • FIG. 4 (B) shows the CO 2 / H 2 selectivity of the samples S1 and C1 as a graph.
  • FIGS. 4 (A) and 4 (B) indicate the CO 2 permeances of sample S1 and sample C1, respectively, and the black squares ( ⁇ ) and white squares ( ⁇ ) indicate H 2 of samples S1 and sample C1. The permeances are shown respectively, and the black triangles ( ⁇ ) and white triangles ( ⁇ ) in FIG. 4 (B) show the CO 2 / H 2 selectivity of the samples S1 and C1, respectively.
  • the horizontal axes of FIGS. 4 (A) and 4 (B) indicate the elapsed time from the start of the experiment.
  • H 2 permeance of samples S1 when compared with H 2 permeance of sample C1, with respect to substantially the same or slightly larger, CO 2 permeance of samples S1 is different from the CO 2 permeance of Sample C1
  • the elapsed time increased 1.6 times or more
  • the addition of silica gel particles to the gel film increased the CO 2 permeance compared to the case without addition, resulting in CO 2 / H. 2
  • the selectivity is greatly improved.
  • the CO 2 / H 2 selectivity of the sample S1 does not change significantly with the passage of time, whereas the CO 2 / H 2 selectivity of the sample C1 tends to decrease with the passage of time.
  • FIG. 5 is a graph showing the CO 2 / H 2 selectivity of samples S2 to S6 and C2 after 1 hour. The horizontal axis of FIG. 5 shows the amount of silica gel particles added (% by weight based on the total weight of the sol solution excluding the hygroscopic agent).
  • Example 1 in which the silica gel particles were added into the gel film, when the addition amount of the silica gel particles was in the range of 0.01% by weight to 0.1% by weight, the addition amount of the silica gel particles increased. , CO 2 / H 2 selectivity tends to increase gradually.
  • FIG. 6 (A) shows the CO 2 permeance and the H 2 permeance of the samples G1 and C3 as a graph
  • FIG. 6 (B) shows the CO 2 / H 2 selectivity of the samples G1 and C3 as a graph.
  • FIGS. 6 (A) and 6 (B) indicate the CO 2 permeances of sample G1 and sample C3, respectively, and the black squares ( ⁇ ) and white squares ( ⁇ ) indicate H 2 of samples G1 and sample C3, respectively.
  • the permeances are shown respectively, and the black triangles ( ⁇ ) and white triangles ( ⁇ ) in FIG. 6 (B) show the CO 2 / H 2 selectivity of the samples G1 and C3, respectively.
  • the horizontal axes of FIGS. 6 (A) and 6 (B) indicate the elapsed time from the start of the experiment.
  • H 2 permeance of samples G1 when compared with H 2 permeance of samples C3, against going slightly larger over time CO 2 permeance of samples G1 is CO 2 samples C3 permeance
  • the elapsed time increased significantly from 1 hour to 1.5 hours by about 1.6 to 4.4 times, and after the elapsed time was 1 hour or later, the surface of the gel film with a surfactant was applied.
  • the CO 2 permeance is increased as compared with the case where the surface is not modified, and as a result, the CO 2 / H 2 selectivity is greatly improved. I understand.
  • the CO 2 permeance of the sample G1 does not change significantly with the passage of time, whereas the CO 2 permeance of the sample C3 tends to decrease significantly with the passage of time. Further, the CO 2 / H 2 selectivity of the sample G1 did not change significantly with the passage of time, and further, a high value of about 350 to 400 could be maintained at a temperature of 160 ° C.
  • FIG. 7 is a graph showing the CO 2 / H 2 selectivity of the samples G2 to G7 and C2 after 1 hour.
  • the horizontal axis of FIG. 7 shows the amount of the surface-modified graphite particles added (% by weight based on the total weight of the sol solution excluding the hygroscopic agent).
  • Example 2 in which the graphite particles subjected to the surface modification treatment were added to the gel film, CO was added in the range of 0.01% by weight to 0.04% by weight of the graphite particles. It can be seen that there is a maximum value of 2 / H 2 selectivity.
  • the addition amount of graphite particles increased by more than 0.04% by weight, the CO 2 / H 2 selectivity tended to decrease, and the same as in Example 1 in which silica gel particles were added.
  • the effect is exhibited even when the amount of the particulate hygroscopic agent added is small.
  • FIG. 8 is a cross-sectional view schematically showing a schematic structure of the CO 2 separation device 10 of the present embodiment.
  • FIG. 8 shows a cross-sectional structure in a cross section perpendicular to the axis of the CO 2 promoted transport membrane (this accelerated transport membrane) 11 having a cylindrical structure
  • FIG. 8 (b) shows the axis of the main promoted transport membrane 11. The cross-sectional structure in the cross section passing through the center is shown.
  • the accelerated transport film 11 shown in FIG. 8 has a structure in which a gel film 1 is supported on an outer peripheral surface of a cylindrical hydrophilic ceramic porous film 2.
  • the gel film 1 the polyvinyl alcohol-polyacrylic acid (PVA / PAA) salt copolymer is used as an example of the film material of the gel film as in the first embodiment, and the gel film 1 is used as a CO 2 carrier.
  • alkali metal carbonates such as cesium carbonate (Cs 2 CO 3 ) and rubidium carbonate (Rb 2 CO 3
  • surface modification treatment with silica gel particles and surfactant was performed as a particulate hygroscopic agent.
  • Use graphite particles Since the method for producing the gel film 1 and the film performance of the second embodiment are basically the same as those of the first embodiment, redundant description will be omitted.
  • the cylindrical main accelerated transport membrane 11 is housed in a bottomed cylindrical container 12, a supply side space 13 surrounded by an inner wall of the container 12 and a gel film 1, and a ceramic porous membrane.
  • a transmissive side space 14 surrounded by the inner wall of No. 2 is formed.
  • a first inlet 15 for feeding the raw material gas FG into the supply side space 13 and a sweep gas SG A second inlet 16 is provided to feed the CO 2 into the permeation side space 14, and the raw material gas EG after CO 2 is separated is discharged from the supply side space 13 on the other side of the bottoms 12a and 12b on both sides of the container 12.
  • a first exhaust port 17 is provided, and a second exhaust port 18 is provided to discharge the exhaust gas SG', which is a mixture of the permeated gas PG containing CO 2 that has permeated the accelerated transport film 11 and the sweep gas SG, from the permeation side space 14.
  • the container 12 is made of stainless steel, for example, and is not shown, but has been described in the first embodiment as an example between both ends of the accelerated transport film 11 and the inner walls of the bottoms 12a and 12b on both sides of the container 12. Similar to the experimental device, the fluororubber gasket is interposed as a sealing material to fix the accelerated transport film 11 in the container 12.
  • the method for fixing and sealing the accelerated transport membrane 11 is not limited to the above method.
  • the first inlet 15 and the first outlet 17 are provided one by one in the supply side space 13 which is separated into left and right in FIG. 8 (b).
  • the supply side space 13 communicates in an annular shape, so that the first inlet 15 and the first discharge port 17 are connected to either the left or right supply side space 13. It may be provided.
  • a first inlet 15 and a second inlet 16 are provided on one side of the bottoms 12a and 12b, and a first outlet 17 and a second outlet are provided on the other side of the bottoms 12a and 12b.
  • the first inlet 15 and the second discharge port 18 are provided on one side of the bottoms 12a and 12b, and the first discharge port 17 and the second discharge port 17 and the second are provided on the other side of the bottoms 12a and 12b.
  • the inlet 16 may be provided. That is, the flow directions of the raw material gases FG and EG and the flow directions of the sweep gas SG and the exhaust gas SG'may be reversed.
  • the raw material gas FG is fed into the supply side space 13 to supply the raw material gas FG to the supply side surface of the promotion transport membrane 11, and is included in the gel film 1 of the promotion transport membrane 11.
  • the CO 2 carrier is reacted with CO 2 in the raw material gas FG to selectively permeate CO 2 with a high selectivity for the main component gas, and the raw material gas EG with an increased concentration of the main component gas after CO 2 separation is supplied. It is discharged from the side space 13.
  • the reaction between CO 2 and CO 2 carriers requires the supply of water (H 2 O) as shown in the reaction formula of (Chemical Formula 1) above, and the more water contained in the gel film 1, the more the chemical equilibrium. Is shifted to the product side (right side), and it can be seen that the permeation of CO 2 is promoted.
  • the temperature of the raw material gas FG is as high as 100 ° C. or higher
  • the gel film 1 in contact with the raw material gas FG is also exposed to a high temperature of 100 ° C. or higher, so that the water contained in the gel film 1 evaporates. Since it penetrates into the transmission side space 14 like CO 2, it is necessary to supply steam (H 2 O) to the supply side space 13.
  • the steam may be contained in the raw material gas FG, or may be supplied to the supply side space 13 separately from the raw material gas FG. In the latter case, the transmitted Steam (H 2 O) was separated from the exhaust gas SG 'to the permeate side space 14 may be circulated to the feed-side space 13.
  • the supply side space 13 is formed on the outside of the cylindrical main promotion transport film 11 and the transmission side space 14 is formed on the inside has been described, but the supply side space is inside. 13 may be formed, and the transmission side space 14 may be formed on the outside.
  • the accelerated transport film 11 may have a structure in which the gel film 1 is supported on the inner peripheral surface of the cylindrical hydrophilic ceramic porous film 2.
  • the accelerated transport membrane 11 used in the CO 2 separation device is not limited to a cylindrical shape, but may be a cylindrical shape having a cross-sectional shape other than a circular shape, and further has a flat plate type structure as shown in FIG. This accelerated transport membrane may be used.
  • CO transformer CO 2 permeation type membrane reactor
  • the supply side space 13 is filled with a CO transformation catalyst, and the supply side space 13 is used as a CO transformer. Can be done.
  • the CO 2 permeation type membrane reactor receives, for example, a raw material gas FG containing H 2 as a main component generated by a steam reformer into a supply side space 13 filled with a CO transformation catalyst and is contained in the raw material gas FG.
  • This is an apparatus for removing carbon monoxide (CO) by the CO transformation reaction shown in (Chemical Formula 4) below.
  • CO carbon monoxide
  • the CO 2 produced by the CO transformation reaction is selectively permeated through the permeation side space 14 by the accelerated transport film 11 to be removed, thereby shifting the chemical equilibrium of the CO transformation reaction to the hydrogen generation side. It is possible to remove CO and CO 2 at a high conversion rate at the same reaction temperature beyond the limit due to equilibrium restrictions.
  • the raw material gas EG mainly of H 2 after removal of CO and CO 2 are removed from the feed-side space 13.
  • the operating temperature is considered to be at least 100 ° C.
  • the supply of the raw material gas FG supplied to the supply side surface of the accelerated transport membrane 11 The temperature is 100 ° C. or higher. Therefore, the raw material gas FG is adjusted to a temperature suitable for the catalytic activity of the CO transformation catalyst, and then sent into the supply side space 13 filled with the CO transformation catalyst, and the CO transformation reaction in the supply side space 13 ( It is supplied to the accelerated transport film 11 via an exothermic reaction).
  • the sweep gas SG lowers the partial pressure of the permeated gas PG containing CO 2 that has permeated the facilitating transport film 11, maintains the permeation propulsive force of the facilitating transport film 11, and discharges the permeated gas PG to the outside. Used to do.
  • the partial pressure of the raw material gas FG is sufficiently high, it is not necessary to flow the sweep gas SG because the partial pressure difference that becomes the permeation propulsion force can be obtained without flowing the sweep gas SG.
  • the gas species used in the sweep gas SG in the same manner as in the evaluation experiments of the membrane performance of the first embodiment, can also use the steam (H 2 O), also further, Ar or the like inert gas used
  • the sweep gas SG is not limited to a specific gas type.
  • a PVA / PAA salt copolymer hydrogel was assumed as the hydrophilic polymer constituting the gel film of the accelerated transport film, but the hydrophilic polymer was used.
  • the hydrophilic polymer was used.
  • the hydrophilic polymer constituting the gel film of the accelerated transport film is not limited to the hydrophilic polymers exemplified in Examples 1 and 2 above.
  • Examples 1 and 2 of the first embodiment it is assumed that cesium carbonate is used as the CO 2 carrier, but in the present invention, a CO 2 carrier and a particulate hygroscopic agent are formed on a gel film of a hydrophilic polymer.
  • the particle-like hygroscopic agent promotes the reaction between CO 2 and CO 2 carriers, which is equivalent to the membrane performance (CO 2 permit and CO 2 selective permeability) exemplified in the first embodiment.
  • Any CO 2 carrier capable of exhibiting a degree or higher film performance is not limited to a specific CO 2 carrier.
  • Examples 1 and 2 of the first embodiment it is assumed that porous particles such as silica gel and graphite are used as the particulate hygroscopic agent, but CO is produced by the particulate hygroscopic agent in the gel film.
  • the material of the particulate hygroscopic agent is not limited to silica gel and graphite as long as it has the same hygroscopicity, and may be a silicon compound such as zeolite other than silica gel, other than graphite. It may be a carbon-based powder such as activated carbon.
  • the specific surface area of the particles is large, but the particles do not necessarily have to be porous, and may have a shape having many protrusions on the surface, for example. ..
  • the upper limit of the distribution range of the particle size of the gel film thickness may be larger than 75 ⁇ m depending on the gel film thickness.
  • a sol solution composed of an aqueous solution containing a PVA / PAA salt copolymer, a CO 2 carrier, and a particulate hygroscopic agent is prepared. Then, the sol solution was cast on the hydrophilic PTFE porous membrane and then gelled to prepare the sol solution, but it may be prepared by a production method other than the production method. For example, a gel film of a PVA / PAA salt copolymer containing a particulate hygroscopic agent and not containing a CO 2 carrier may be formed and then impregnated with an aqueous solution containing a CO 2 carrier.
  • the step of preparing the sol solution the case where the hydrophilic polymer and the CO 2 carrier are added to the pure water to which the particulate hygroscopic agent is added first has been illustrated. And CO 2 carriers may be added to pure water at the same time to prepare a sol solution. Further, a gel film prepared by casting a sol solution prepared by simultaneously adding a particulate hygroscopic agent and a hydrophilic polymer to pure water into a hydrophilic PTFE porous film and then gelling the gel film contains an aqueous solution containing a CO 2 carrier. It may be invaded and produced.
  • the CO 2 separation device using this facilitated transport membrane As one application of the CO 2 separation device using this facilitated transport membrane has been described CO 2 permeable membrane reactor, the CO 2 separation device using this facilitated transport membrane, It can be used in a decarboxylation step in a hydrogen production process other than the membrane reactor, and further, it can be applied to other than the hydrogen production process, and is limited to the application examples exemplified in the second embodiment. is not it. Further, the supply-side gas (raw material gas) supplied to the accelerated transport membrane is not limited to the mixed gas exemplified in each of the above embodiments.
  • the main component gas of the mixed gas is not limited to hydrogen (H 2 ), but nitrogen (N 2 ), methane (CH 4 ), and oxygen (CH 4), which permeate this accelerated transport membrane only by the dissolution / diffusion mechanism. It may be O 2 ) or the like.
  • CO 2 facilitated transport membrane according to the present invention, as an example, decarboxylation process of hydrogen production process, in CO 2 permeable membrane reactor, etc., the CO 2 with high selectivity against hydrogen ratio from a mixed gas containing CO 2 and H 2 It can be used to separate.

Landscapes

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

Abstract

L'invention concerne une membrane de transport facilité de CO2 possédant une perméance au CO2 et une perméabilité sélective au CO2. La membrane de transport facilitée de CO2 est formée de manière à contenir un support de CO2 et un agent d'absorption d'humidité particulaire à l'intérieur d'une membrane de gel polymère hydrophile. De préférence, l'agent d'absorption d'humidité est formé à partir de particules poreuses et est présent à l'intérieur de la membrane de gel d'une manière dispersée. De préférence, la membrane de gel est un hydrogel. De préférence, la membrane de gel est supportée par une membrane poreuse hydrophile.
PCT/JP2020/032069 2019-10-23 2020-08-25 Membrane de transport facilitée de co2, son procédé de production et procédé et dispositif de séparation de co2 WO2021079609A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2021554109A JP7161253B2 (ja) 2019-10-23 2020-08-25 Ｃｏ２促進輸送膜及びその製造方法並びにｃｏ２分離方法及び装置

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2019-192862 2019-10-23
JP2019192862 2019-10-23

Publications (1)

Publication Number Publication Date
WO2021079609A1 true WO2021079609A1 (fr) 2021-04-29

Family

ID=75620461

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2020/032069 WO2021079609A1 (fr) 2019-10-23 2020-08-25 Membrane de transport facilitée de co2, son procédé de production et procédé et dispositif de séparation de co2

Country Status (2)

Country Link
JP (1) JP7161253B2 (fr)
WO (1) WO2021079609A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013027841A (ja) * 2011-07-29 2013-02-07 Fujifilm Corp 二酸化炭素分離部材、その製造方法及び二酸化炭素分離モジュール
JP2016041415A (ja) * 2013-12-26 2016-03-31 富士フイルム株式会社 酸性ガス分離モジュール
WO2017154519A1 (fr) * 2016-03-09 2017-09-14 株式会社ルネッサンス・エナジー・リサーチ Système de combustion

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013027841A (ja) * 2011-07-29 2013-02-07 Fujifilm Corp 二酸化炭素分離部材、その製造方法及び二酸化炭素分離モジュール
JP2016041415A (ja) * 2013-12-26 2016-03-31 富士フイルム株式会社 酸性ガス分離モジュール
WO2017154519A1 (fr) * 2016-03-09 2017-09-14 株式会社ルネッサンス・エナジー・リサーチ Système de combustion

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JAHAN, ZAIB ET AL.: "Cellulose nanocrystal/PVA nanocomposite membranes for C02/ CH 4 separation at high pressure", JOURNAL OF MEMBRANE SCIENCE, vol. 554, 6 March 2018 (2018-03-06), pages 275 - 281, XP055819511 *

Also Published As

Publication number Publication date
JP7161253B2 (ja) 2022-10-26
JPWO2021079609A1 (fr) 2021-04-29

Similar Documents

Publication Publication Date Title
JP5796136B2 (ja) Ｃｏ２促進輸送膜及びその製造方法並びにｃｏ２分離方法及び装置
JP5553421B2 (ja) Ｃｏ２促進輸送膜及びその製造方法
EP2239048B1 (fr) Membrane à transport facilité du co2 et procédé de fabrication de celle-ci
JP5555332B2 (ja) ガス分離装置、メンブレンリアクター、水素製造装置
JP6294304B2 (ja) Ｃｏ２促進輸送膜、その製造方法及び当該製造方法に用いられる樹脂組成物、並びに、ｃｏ２分離モジュール、ｃｏ２分離方法及び装置
JP5996742B2 (ja) 促進輸送膜の製造方法
WO2021079609A1 (fr) Membrane de transport facilitée de co2, son procédé de production et procédé et dispositif de séparation de co2
Okada et al. CO2-facilitated transport membrane and method for producing the same

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20879990

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2021554109

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20879990

Country of ref document: EP

Kind code of ref document: A1