WO2023084865A1 - Membrane de transport facilité par co2, procédé de séparation de co2, et procédé de production de membrane de transport facilité par co2 - Google Patents

Membrane de transport facilité par co2, procédé de séparation de co2, et procédé de production de membrane de transport facilité par co2 Download PDF

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WO2023084865A1
WO2023084865A1 PCT/JP2022/031847 JP2022031847W WO2023084865A1 WO 2023084865 A1 WO2023084865 A1 WO 2023084865A1 JP 2022031847 W JP2022031847 W JP 2022031847W WO 2023084865 A1 WO2023084865 A1 WO 2023084865A1
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facilitated transport
gel
organic solvent
transport membrane
water
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PCT/JP2022/031847
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English (en)
Japanese (ja)
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治 岡田
泰 藤澤
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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    • 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
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • 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
    • 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
    • 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
    • B01D71/08—Polysaccharides
    • B01D71/12—Cellulose derivatives
    • 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
    • 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
    • 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
    • B01D71/74—Natural macromolecular material or derivatives thereof
    • 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

Definitions

  • the present invention relates to a CO 2 -facilitated transport membrane used for the separation of carbon dioxide (CO 2 ), and in particular, separates carbon dioxide from a mixed gas containing carbon dioxide under energy-saving operating conditions such as room temperature, normal pressure, and low humidity. and a CO 2 separation method using the CO 2 facilitated transport membrane.
  • CO 2 carbon dioxide
  • CO2 - facilitated transport membranes are constructed by incorporating, within the matrix material of the membrane, a CO2 carrier that reversibly and selectively reacts with carbon dioxide.
  • Carbon dioxide is introduced into the membrane mainly by reacting with the CO2 carrier to form a reaction product, and moves through the membrane as a reaction product (facilitated transport mechanism) to reach other membrane surfaces, Carbon dioxide is separated and released outside the membrane by decomposition of the reaction products into carbon dioxide and a CO2 carrier.
  • Nitrogen, oxygen, hydrogen, methane, etc. that do not react with the CO2 carrier permeate through the membrane by a dissolution-diffusion mechanism, so the permeance of carbon dioxide is the same as that of nitrogen, oxygen, hydrogen, methane, etc. that do not react with the CO2 carrier. Since it is greater than the permeance, expression of very high selectivity is expected.
  • a CO 2 separation process using a CO 2 facilitated transport membrane separates gas species based on the difference in permeation rates through different membranes.
  • the driving force behind the velocity difference is the partial pressure difference between the gas species on both sides of the membrane, and the larger the partial pressure difference, the higher the permeation velocity.
  • the energy (exothermic reaction) generated during the reaction of the reaction product from carbon dioxide and CO2 carrier when carbon dioxide is absorbed into the membrane is significantly different from other membranes in very thin membranes ( ⁇ tens of ⁇ m).
  • the reaction product is decomposed into carbon dioxide and CO 2 carrier on the surface, and the energy (endothermic reaction) required for releasing carbon dioxide is used, so there is no need to supply energy from the outside. Therefore, the CO2 separation process using CO2 - facilitated transport membranes is essentially an energy-saving process.
  • CO2 carrier of the CO2 - facilitated transport membrane of the water-based gel membrane There are many candidates for the CO2 carrier of the CO2 - facilitated transport membrane of the water-based gel membrane.
  • Alkali metal salts carbonates, bicarbonates, hydroxides
  • carbonates, bicarbonates, hydroxides such as are commonly used.
  • Preferable operating conditions for promoting the carrier reaction include, for example, a temperature higher than room temperature by 80°C or higher, and a CO2 partial pressure difference between the feed side and the permeate side of the CO2 facilitated transport membrane. It is implemented to pressurize the feed side of the CO2- facilitated transport membrane or depressurize the permeate side, and to maintain high humidity (eg, relative humidity of 70% or more) to prevent drying inside the membrane. ing.
  • Patent Document 5 a water-based gel membrane CO 2- facilitated transport membrane that operates at normal temperature and pressure is proposed. It is necessary to supply water from the membrane to maintain the water content in the membrane. This point is the same as the CO 2 -facilitated transport membranes of water-based gel membranes disclosed in Patent Documents 1 to 4 above.
  • the present invention provides a CO 2 -facilitated transport membrane that does not require external water supply, which is essential for conventional CO 2 -facilitated transport membranes, or can be greatly reduced.
  • An object of the present invention is to provide an energy-saving CO 2 separation process using the CO 2 -facilitated transport membrane.
  • the present invention provides a CO2- facilitated transport membrane comprising a gel membrane of a polymer compound and an organic solvent, wherein the gel membrane contains a CO2 carrier.
  • the gel film of the polymer compound and the organic solvent is a gel of a mixed solution of the polymer compound and the organic solvent.
  • a CO2 carrier that selectively reacts with organic solvents and carbon dioxide in . Due to the presence of the organic solvent in the gel film, the reaction between carbon dioxide and the CO 2 carrier proceeds without an external moisture supply or even with limited water supply, and the reaction product is the organic solvent. Even a small CO2 partial pressure difference can move from the feed side to the permeate side of the CO2- facilitated transport membrane.
  • the CO 2 -facilitated transport membrane of the water-based gel membrane containing no organic solvent in the gel membrane even under operating conditions in which carbon dioxide cannot sufficiently permeate, the CO 2 -facilitated transport membrane with the above characteristics A large CO2 permeance and high selectivity to gases that do not react with the CO2 carrier can be achieved.
  • the organic solvent is at least one organic solvent selected from alcoholic organic solvents and aprotic organic solvents.
  • the alcoholic organic solvent is 1,3-butanediol, 1,4-butanediol, ethylene glycol, polyethylene glycol (PEG), ethanol, At least one of isopropyl alcohol (IPA), glycerin, and the aprotic organic solvent is acetone, ethyl methyl ketone, 1,4-dioxane, dimethylsulfoxide (DMSO), N,N-dimethylformamide (DMF). , N-methyl-2-pyrrolidone (NMP).
  • the polymeric compounds include polyvinyl alcohol (PVA), vinyl acetate, polypropylene glycol, polyacrylic acid (PAA), polyethylene glycol (PEG), and poly First candidate group of synthetic polymers containing allylamine, second candidate group of natural polymers containing pectin, chitosan, agarose, starch paste, xanthan gum, duran gum, and alginic acid, and carboxymethylcellulose and hydroxypropyl At least one polymer compound selected from the third candidate group of semi-synthetic polymer systems containing cellulose (HPC).
  • PVA polyvinyl alcohol
  • PAA polyacrylic acid
  • PEG polyethylene glycol
  • second candidate group of natural polymers containing pectin, chitosan, agarose, starch paste, xanthan gum, duran gum, and alginic acid and carboxymethylcellulose and hydroxypropyl
  • HPC semi-synthetic polymer systems
  • the polymer compound is a hydrophilic polymer compound
  • the organic solvent is an alcoholic organic solvent or an aprotic organic solvent.
  • the CO2 carrier comprises alkali metal carbonates, alkali metal bicarbonates, alkali metal hydroxides, amino acids, monovalent organic amines, and at least one of organic polyhydric amines.
  • the gel film contains water, and the water content Xm based on the total weight of the organic solvent and the water is 0. ⁇ Xm ⁇ 20 (% by weight).
  • the amount of water present in the gel film is small compared to the organic solvent and is not dominant. effect is not hindered.
  • the present invention uses the CO 2 facilitated transport membrane having the above characteristics to supply a mixed gas containing a predetermined main component gas and CO 2 to the CO 2 facilitated transport membrane, and from the mixed gas A method for separating CO2 is provided, wherein the CO2 that has permeated the CO2 - facilitated transport membrane is separated.
  • the CO 2 separation method having the above characteristics, even if the mixed gas does not contain water, or even if it does contain water, the amount of water is less than the CO 2 facilitated transport membrane of the conventional water-based gel membrane. Carbon dioxide in the mixed gas can be separated with high selectivity with respect to the main component gas even if the amount of water supplied from the outside is smaller than that required for the CO 2 separation method used. As a result, an energy-saving CO 2 separation process can be provided because the supply of water from the outside is unnecessary or can be greatly reduced.
  • the mixed gas is supplied to the CO 2 facilitated transport membrane within a temperature range of 10°C or higher and 50°C or lower.
  • the CO 2 facilitated transport membrane does not need to be used at a high temperature of, for example, 80° C. or higher, and the energy required for heating can be eliminated or significantly reduced, and a further energy-saving CO 2 separation process can be provided. can.
  • the pressure difference between the feed side and the permeate side of the CO2 facilitated transport membrane is 100 kPa or less.
  • the energy required for pressurizing the feed side of the CO2 - facilitated transport membrane or decompressing the permeate side, etc. can be greatly reduced as the usage environment of the CO2- facilitated transport membrane, and a further energy-saving CO2 separation process can be realized. can provide.
  • the pressure difference is preferably 30 kPa or less, more preferably 15 kPa or less.
  • the relative humidity of the mixed gas on the feed side of the CO 2 facilitated transport membrane is 0% or more and less than 50%. This relative humidity specifically indicates that the supply of moisture from the outside is unnecessary or can be greatly reduced.
  • the present invention provides a method for producing a CO 2 -facilitated transport membrane having the above characteristics, comprising the steps of preparing a gel-like mixture containing the organic solvent, the polymer compound, and the CO 2 carrier; and applying the gel-like mixture onto the surface of a support to produce the gel membrane.
  • a large amount of CO A CO2 facilitated transport membrane can be provided that can exhibit 2 permeance and high selectivity to gases that do not react with the CO2 carrier.
  • a mixed solution obtained by adding the polymer compound to the organic solvent is stirred. It is gelled to prepare an intermediate gel-like substance, and the CO 2 carrier is added to the intermediate gel-like substance and stirred to prepare the gel-like mixture.
  • the organic solvent and purified water are used in the step of preparing the gel-like mixture.
  • a second feature is to prepare a gel-like mixture containing the polymer compound and the CO2 carrier.
  • the content of the purified water Xm based on the total weight of the organic solvent and the purified water is 0 ⁇ Xm ⁇ 20 (% by weight).
  • a large amount of CO CO2 - facilitated transport membranes with water in gel membranes can be provided that can exhibit 2 permeance and high selectivity to gases that do not react with the CO2 carrier.
  • a mixed solution is obtained by adding the purified water and the polymer compound to the organic solvent. is stirred and gelled to prepare an intermediate gel-like material, and the CO 2 carrier is added to the intermediate gel-like material and stirred to prepare the gel-like mixture.
  • CO 2 -facilitated transport membrane and the manufacturing method thereof having the above characteristics a CO 2 -facilitated transport membrane that does not require external water supply, which is essential for conventional CO 2 -facilitated transport membranes, or can be greatly reduced is provided. Furthermore, according to the CO 2 separation method having the above characteristics, an energy-saving CO 2 separation process using the CO 2 facilitated transport membrane can be provided.
  • FIG. 5 is a graph showing the relationship between CO 2 permeance and CO 2 partial pressure in Examples 4 and 5;
  • FIG. 4 is a graph showing the relationship between the N2 permeance and the N2 partial pressure in Examples 4 and 5;
  • FIG. 4 is a graph showing the relationship between CO 2 permeance and relative humidity in Comparative Example 1.
  • FIG. 11 is a graph showing the relationship between CO 2 permeance and relative humidity in Example 11;
  • FIG. 2 is an explanatory diagram schematically showing the flow of gas in an embodiment by the sweep gas method of the CO 2 separation method according to the present invention.
  • FIG. 2 is an explanatory diagram schematically showing the flow of gas in one embodiment of the CO 2 separation method according to the present invention by the depressurization method;
  • the facilitated transport film is characterized by including a CO 2 carrier in a gel film of a polymer compound and an organic solvent.
  • CO2 - facilitated transport membranes which include CO2 carriers and moisture in hydrophilic polymer gel membranes, it is significantly different in that the gel membranes contain an organic solvent. Due to the unique structure of this facilitated transport membrane, in which an organic solvent is contained in the gel membrane, as will be described later, the external supply of water, which was essential in conventional CO2 facilitated transport membranes, is unnecessary or can be greatly reduced. It is possible to obtain a remarkable effect peculiar to the present facilitated-transport membrane that a CO 2 -facilitated-transport membrane can be provided.
  • a gel film is a polymer compound that is almost uniformly swollen or dissolved in a solvent, and refers to a film formed of a material (gel) that has poor fluidity compared to the case of using a solvent alone.
  • Candidates for the polymer compound are not particularly limited as long as they can form a gel with an organic solvent, but the first group of synthetic polymer candidates, the second group of natural polymer candidates, and At least one polymer compound selected from the third candidate group of modified polysaccharides is preferable because it easily forms a gel with the organic solvent.
  • the high-molecular compound of the first candidate group is a compound (polyolefin-based or polyether-based) polymerized by a C--C or C--O bond, and is therefore highly stable and therefore preferred.
  • a polymer compound that easily forms a water-based gel is preferred because it is particularly easy to form a gel with an organic solvent (alcohol-based).
  • First candidate group Polyvinyl alcohol (PVA), vinyl acetate, polypropylene glycol, polyacrylic acid (PAA), polyacrylic acid (slightly crosslinked), polyethylene glycol (PEG), and the like.
  • Second candidate group Natural polymer “polysaccharides”): Pectin, chitosan, agarose, starch paste, xanthan gum, duran gum, alginic acid, etc.
  • Third candidate group si-synthetic polymer system “modified polysaccharides”: Carboxymethyl cellulose, hydroxypropyl cellulose (HPC), cellulose acetate, and the like.
  • Candidates for the organic solvent are not particularly limited as long as they can form a gel with the polymer compound. At least one organic solvent selected from is preferable because it easily forms a gel. Further, among the organic solvents of the first candidate group, alcohols (polyhydric alcohols) having a plurality of hydroxyl groups, such as 1,3-butanediol, 1,4-butanediol, and ethylene glycol, are particularly suitable for polymer compounds. It is preferable because it easily interacts with the functional group to form a gel stably.
  • First candidate group (alcohol solvent): 1,3-butanediol, 1,4-butanediol, ethylene glycol, polyethylene glycol (PEG), ethanol, isopropyl alcohol (IPA), glycerin, and the like.
  • Second candidate group (aprotic solvent) ⁇ Ketone series: acetone, ethyl methyl ketone, etc.
  • Ether type 1,4-dioxane, tetrahydrofuran, diethyl ether, and the like.
  • Others dimethylsulfoxide (DMSO), N,N-dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP), and the like.
  • Polyethylene glycol (PEG) is included in both the first candidate group of polymer compounds and the first candidate group of organic solvents. It is about 100 to 10,000 times larger than the molecular weight of polyethylene glycol as a candidate for .
  • the number average molecular weight (Mn) of polyethylene glycol as a candidate for the polymer compound is, for example, about 10,000 to several million, and the number average molecular weight (Mn) of polyethylene glycol as a candidate for the organic solvent is, for example, 100 to 300. degree.
  • the CO2 carrier basically, the CO2 carrier used in the conventional water-based gel membrane CO2 - facilitated transport membrane can be used as it is.
  • candidates for the CO2 carrier include alkali metal carbonates, alkali metal bicarbonates, alkali metal hydroxides, amino acids, monovalent organic amines, and organic multivalent amines. At least one selected. Among these alkali metals, potassium, rubidium and cesium can be suitably used. Examples of candidates for amino acids, monovalent organic amines, and organic polyvalent amines are given below.
  • amino acids 20 naturally occurring amino acids including arginine and glycine, 2,3-diaminopropionate (DAPA), sarcosine, ornithine, 2-aminobutyric acid, cystine, 3-aminobutyric acid, creatine, citrulline, theanine, ⁇ -alanine, etc. .
  • monovalent organic amines benzylamine, piperidine, hexamethyleneimine, butylamine, hexylamine, octylamine, diisopropylamine, trimethylamine, aniline, pyrrolidine, ethanolamine, dimethylamine, 2-amino-2-hydroxymethyl-1,3-propanediol, and the like.
  • organic polyvalent amines piperazine, ethylenediamine, 1,4-butanediamine, m-xylylenediamine, hexamethylenediamine, diethylenetriamine, phenylenediamine, naphthalenediamine, 1,3-propanediamine, polyethyleneimine, 1,5-pentanediamine, tris(2-amino ethyl)amine, 2-(2-aminoethylamino)ethanol, N,N-dimethyl-1,3-propanediamine, N,N'-dimethyl-1,3-propanediamine, and the like.
  • polymer compounds and organic solvents can be used as the polymer compounds and organic solvents used in the facilitated transport film.
  • conditions for the polymer compound and organic solvent that can be used it is necessary that a gel can be formed between the polymer compound and the organic solvent.
  • Hydrophilic polymer compounds used in conventional water-based gel films form gels by interacting with the hydroxyl groups of water. Easy to form gel.
  • the aprotic solvent of the second candidate group is also polarized (for example, the oxygen atom of the carbonyl group) and has a ⁇ -charge like the oxygen atom of water. It is considered that gels are likely to be formed with protic solvents. All of the polymer compounds of the first to third candidate groups described above are hydrophilic polymer compounds.
  • the blending ratio (weight ratio) of the polymer compound, the organic solvent, and the CO2 carrier in the gel film of the facilitated transport film is suitable according to the polymer compound, the organic solvent, and the CO2 carrier to be used. Since the range and the optimum range vary, each sample of the above nine combinations of Examples 1 to 9 described below uses approximately the same blending ratio in order to compare the performance between samples. However, the blending ratio of the polymer compound, the organic solvent, and the CO2 carrier is not limited to the blending ratio used in the examples. Or it is considered that an optimum value can be set. Each compounding ratio (% by weight) is based on the total weight of the polymer compound, organic solvent, and CO2 carrier.
  • the blending ratio of the polymer compound is too low, it will be difficult to form a gel film that maintains sufficient strength, so the gel film tends to be damaged and leak easily when separating carbon dioxide.
  • the blending ratio of the polymer compound is too large, the polymer compound does not retain sufficient organic solvent, and pinholes tend to occur in the gel film, making leakage more likely. As the amount of polymer compound added increases, the viscosity of the gel film increases.
  • the blending ratio of the organic solvent is too low, pinholes tend to occur in the gel film, and if it is too high, the gel film tends to be damaged. As the amount of the organic solvent added increases, the viscosity of the gel film decreases.
  • the organic solvent one type of organic solvent may be used alone, or two or more types of organic solvents may be mixed and used as a mixed organic solvent.
  • a water-containing mixed solvent in which water is added to one type of organic solvent or a mixed organic solvent may be used.
  • the present facilitated transport film is characterized by containing an organic solvent in the gel film, when a water-containing mixed solvent is used, the organic solvent must be predominantly present in the water-containing mixed solvent.
  • the water content Xm based on the total weight of the mixed solvent (organic solvent + water) is preferably 0 ⁇ Xm ⁇ 20 (% by weight).
  • water-containing mixed solvent means a state in which an organic solvent and water are present in the gel film at the time the gel film is produced, and does not necessarily mean that the organic solvent and water are present in the gel film before the gel film is produced. It does not mean that the aqueous mixed solvent is prepared in advance as a mixed solvent of one type of organic solvent or a mixed organic solvent with water added in the process.
  • the facilitated transport membrane comprises a support carrying a gel membrane containing a CO 2 carrier, and the gel membrane is formed on one side of the support.
  • the facilitated transport film may have a structure in which a gel film is sandwiched between two supports, and the support supporting the gel film may be composed of two or more layers such as a hydrophilic film and a hydrophobic film. A multilayer structure may be used.
  • the support uses a material that can permeate the gas and support the gel membrane, such as a porous membrane or non-woven fabric of any shape such as a flat plate or a cylindrical shape, similar to the CO 2 facilitated transport membrane of the conventional water-based gel membrane. can do.
  • a tetrafluoroethylene polymer (PTFE) porous membrane can be preferably used as an example of the porous membrane.
  • the porous PTFE membrane may be hydrophilic PTFE, hydrophobic PTFE, or a laminate of hydrophilic PTFE and hydrophobic PTFE.
  • an intermediate gel-like substance is prepared by adding a polymer compound to an organic solvent to gel it (step 1). More specifically, a predetermined amount of an organic solvent and a predetermined amount of a polymer compound are weighed and added to a container (for example, a weighing bottle), and stirred at room temperature until a homogeneous gel is formed (for example, about 17 hours or more). to obtain an intermediate gel.
  • a container for example, a weighing bottle
  • step 1 When using a mixed organic solvent by mixing two or more kinds of organic solvents as the organic solvent, in step 1, a predetermined amount of each organic solvent is weighed and added to a container (for example, a weighing bottle), and A fixed amount of polymer compound is weighed and further added to prepare.
  • a container for example, a weighing bottle
  • a CO 2 carrier is added to the intermediate gel and stirred to prepare a gel mixture of the organic solvent, polymer compound and CO 2 carrier (step 2). More specifically, a predetermined amount of CO 2 carrier is weighed and added to the intermediate gel-like substance in the container, and stirred at room temperature for a predetermined time (eg, about 12 hours or more) to obtain a gel-like mixture.
  • a surfactant is added so that a uniform film can be formed in close contact with the support during coating in the next step
  • an antistatic agent is added so that static electricity is less likely to be charged
  • an antistatic agent is added so that it can be stored stably for a long period of time.
  • Various components for imparting predetermined functions such as preservatives and fillers for the purpose of imparting film strength, may be added.
  • the gel-like mixture is coated on one side of the support so as to have a predetermined film thickness to prepare a gel film (step 3). More specifically, for example, the gel mixture is evenly applied on one side of the support with an applicator at room temperature.
  • the support is literally a material for supporting the gel membrane, and corresponds to the porous membrane described above, and generally has a pore diameter of about 10 ⁇ m or less, a porosity of about 90% or less, and a thickness of about 100 ⁇ m.
  • the following porous sheet materials are used.
  • the gel state of the "intermediate gel-like material” and “gel-like mixture” in this production method means a state of a highly viscous, homogeneous substance that has poor fluidity but is deformable.
  • This production method is carried out at room temperature (approximately 18° C. to 28° C.) lower than the boiling point of the organic solvent, and in Steps 1 to 3, there is no drying step at high temperature or low humidity.
  • the organic solvent is retained in the gel film without evaporating.
  • step 1 when the above-described water-containing mixed solvent is used as the organic solvent, in step 1, one or more organic solvents and a polymer compound are mixed in a container (for example, a weighing bottle). , For example, stirring as necessary at room temperature (for example, stirring for about 1 hour), then weighing and adding a predetermined amount of purified water, for example, until the gel is homogenized at room temperature (for example, for about 17 hours or more) ) to obtain an intermediate gel. As a result, in step 2, a gel-like mixture of the organic solvent, water, polymer compound, and CO2 carrier is prepared, and in step 3, a gel film containing the organic solvent, water, polymer compound, and CO2 carrier is obtained. .
  • a container for example, a weighing bottle.
  • evaluation samples of the present facilitated transport membranes (Examples 1 to 21, Examples 1A to 1D, and Examples 2A to 2B) and evaluation samples of CO 2 facilitated transport membranes for comparison (Comparative Examples 1 to 7 ) will be explained.
  • the volume of the container used was 50 mL
  • a magnetic stirrer was used for stirring
  • a hydrophilic PTFE porous membrane (advantech membrane filter , H010A047A) were used.
  • the film thickness of the gel film is 100 ⁇ m in all evaluation samples.
  • Polymer compounds, organic solvents, and CO2 carriers used in the evaluation samples of Examples and Comparative Examples are listed below.
  • Polymer compounds are 6 types indicated by identification symbols A1 to A6, organic solvents are 7 types indicated by identification symbols B1 to B7 (including those used in mixed organic solvents and aqueous mixed solvents), CO 2 carrier are 15 types indicated by identification symbols C1 to C15.
  • ⁇ Polymer compound> A1: Polyacrylic acid (slightly cross-linked), Akpec (HV-501) manufactured by Sumitomo Seika
  • A2: Polyacrylic acid (PAA), Mn 1,000,000
  • A4: Polyethylene glycol (PEG), Mn 4 million
  • A5: Polyallylamine hydrochloride, MW 120,000 to 200,000
  • A6 Xanthan gum
  • A1, A2, A4, and A5 are synthetic polymer systems
  • A3 is a semi-synthetic polymer system
  • A6 is a natural polymer system.
  • B1, B4 and B6 are alcoholic solvents, and B2, B3, B5 and B7 are aprotic solvents.
  • C5 and C8 are alkali metal carbonates
  • C6, C7 and C14 are amino acids
  • C2 and C11 are monovalent organic amines
  • C1, C3, C4, C9, C10, C12, C13 and C15 are It is an organic polyvalent amine.
  • compositions of the gel films of Examples and Comparative Examples are shown in Tables 1 to 3 below, using respective identification symbols for the polymer compound, organic solvent, and CO 2 carrier described above.
  • the identification symbol W in the solvent column in Tables 2 and 3 indicates water (purified water).
  • the number in parentheses on the right side of each identification symbol is the weight weighed when the evaluation sample was prepared. Furthermore, no additive for accelerating the reaction of the CO 2 carrier or for suppressing functional deterioration was added to the gel film of each sample. For this reason, in this evaluation experiment, we did not use a combination of multiple CO 2 carriers.
  • Examples 1 to 8, 13, and 14, as shown in Table 1, include any one of polymer compounds A1 to A3, any one of organic solvents B1 to B6, and any one of CO 2 carriers C1 to C7.
  • Example 9, as shown in Table 1, is a sample having a gel film produced by combining polymer compound A1, mixed organic solvent of organic solvents B1 and B6, and CO2 carrier C8.
  • Examples 10 to 12, 15 to 21, Examples 1A to 1D, and Examples 2A to 2B are, as shown in Table 2, any one of polymer compounds A1 and A4 and organic solvents B1, B2, and B7.
  • a sample having a gel film prepared by combining any one of the water-containing mixed solvent and water (purified water) with any one of the CO 2 carriers C1, C2, and C8 to C15.
  • the water content Xm based on the total weight of the water-containing mixed solvent is set within the range of 4 to 17% by weight. These samples were prepared for the purpose of examining the effect of partial water inclusion under the condition that the organic solvent is predominant in the gel film.
  • the water content Xm (% by weight) is represented by the following (Equation 1).
  • Examples 1A to 1D are samples in which part of the organic solvent B1 of Example 1 is replaced with water, and the water content Xm differs between Examples 1A to 1D.
  • the weight of the organic solvent B1 in the gel film of Example 1 and the weight of the water-containing mixed solvent (B1+W) in the gel films of Examples 1A to 1D were unified at 4.8 g.
  • Examples 2A and 2B are samples in which part of the organic solvent B2 of Example 2 is replaced with water, and the water content Xm differs between Examples 2A and 2B.
  • the weight of the organic solvent B2 in the gel film of Example 2 and the weight of the water-containing mixed solvent (B2+W) in the gel films of Examples 2A and 2B were unified at 4.6 g.
  • Example 13 polyallylamine hydrochloride, which is a polymer compound, is gelled with liquid ethylenediamine, which is a CO2 carrier. has been added.
  • Examples 20 and 21 are gels of the same composition as Example 10 (polymer compound+organic solvent+water) with the addition of different amounts of the same CO2 carrier (diethylenetriamine).
  • Comparative Examples 1 to 6 as shown in Table 3, use water instead of the organic solvent, and are classified as water-based gel films used in the conventional CO 2 -facilitated transport films described above.
  • Comparative Example 1 is a sample prepared by using water instead of the organic solvent B1 of Example 4.
  • Comparative Example 2 is a sample prepared by using water instead of the organic solvent B4 of Example 5.
  • Comparative Example 6 is a sample in which no CO 2 carrier was added to the gel film of Comparative Example 1 or Comparative Example 4.
  • Comparative Example 7 is a sample in which CO 2 carrier was not added to the gel film of Example 4.
  • the weight of the gel film (gel-like mixture) was 5.5 g, and the weight of the CO 2 carrier therein was 0.5 g. common.
  • the total weight of the polymer compound and the solvent (water or organic solvent) in the gel film (gel-like mixture) is 5.0 g in common.
  • the drying process at high temperature or low humidity was not performed as in the case of the facilitated transport film.
  • the membrane performance of the CO 2 -facilitated transport membrane was measured separately. Measurement of the membrane performance of the CO2 - facilitated transport membrane was carried out by the sweep gas method using the experimental setup shown in FIG. In the following evaluation experiments, a mixed gas of CO2 and N2 was used as the feed gas FG supplied to the CO2- facilitated transport membrane, and moisture (water vapor) was added to the feed gas FG according to the contents of the evaluation. .
  • the CO 2 -facilitated transport membrane 1 of each sample is sandwiched between two annular gaskets in the first space on the supply side of the flow-through gas permeation cell 2. 3 and a second space 4 on the transmission side.
  • CO 2 and N 2 that make up the feed gas FG join together on the downstream side after passing through a mass flow controller (MFC) and a valve, and then enter the first space 3 of the gas permeation cell 2 as feed gas FG with a predetermined mixing ratio. supplied.
  • MFC mass flow controller
  • the post-processed feed gas EG in the first space 3 that has not passed through the CO 2 -facilitated transport membrane 1 in the feed gas FG passes through the cooling trap 5 provided in the exhaust gas discharge path and the back provided downstream thereof.
  • the pressure in the first space 3 is adjusted with a back pressure regulator 6 .
  • the flow rate of CO 2 and N 2 constituting the feed gas FG and the total pressure of the feed gas FG (the first 1 space 3) is regulated.
  • the CO 2 concentration (dry base) in feed gas FG is approximately 4.5 mol %.
  • the sweep gas SG is supplied to maintain the permeation driving force by lowering the partial pressure of the mixed gas (CO 2 , N 2 ) permeating the CO 2 facilitated transport membrane 1 of the sample on the second space 4 side, A gas type (Ar gas) not included in the feed gas FG is used.
  • Ar gas was supplied to the second space 4 at a flow rate of 20 mL/min.
  • the pressure on the side of the second space 4 is the atmospheric pressure (0 kPa (G), 100 kPa).
  • An exhaust gas MG which is a mixed gas of the sweep gas SG and the gas that has permeated the sample CO 2 -facilitated transport film 1 from the first space 3 side to the second space 4 side, is discharged from the second space 4 .
  • the gas composition is quantified by gas chromatograph 9 (manufactured by Shimadzu Corporation, GC- 8A ) . was calculated, and the CO 2 / N 2 selectivity was calculated from the ratio.
  • the gas permeation cell 2 was placed in a constant temperature bath (electric furnace) set at 30°C in order to keep the operating temperature of the gas permeation cell 2 constant. is temperature controlled. Thereby, the temperature of the feed gas FG supplied into the first space 3 also becomes 30°C. Incidentally, in Evaluation 5, the temperature of the feed gas FG is set to be higher than 30.degree.
  • the membrane performance of Examples 1 to 9 of the facilitated transport membrane is CO 2 permeance: 2.7 ⁇ 10 -6 to 18 ⁇ 10 -6 [mol/(m 2 ⁇ s ⁇ kPa) ], N 2 permeance: 1.0 ⁇ 10 ⁇ 8 to 7.7 ⁇ 10 ⁇ 8 [mol/(m 2 ⁇ s ⁇ kPa)], CO 2 /N 2 selectivity: 110 to 330 are obtained. . It can be seen that this facilitated transport membrane exhibits good CO 2 separation performance due to the CO 2 facilitated transport mechanism even if water vapor is not added to the feed gas FG.
  • Comparative Example 1 is a CO2 - facilitated transport film of a water-based gel film using water instead of the organic solvent B1 in Example 4. Same as 4. Comparative Example 2 is a CO2- facilitated transport film of a water-based gel film using water instead of the organic solvent B4 of Example 5. Same as 5. Therefore, in particular, from the comparison between Example 4 and Comparative Example 1, and between Example 5 and Comparative Example 2, depending on whether the organic solvent or water is present in the gel film, the gel film does not contain water vapor. It can be seen that the CO2 separation performance for the feed gas FG varies dramatically.
  • Comparative Example 6 is a sample in which no CO 2 carrier was added to the gel film of Comparative Example 1 or Comparative Example 4. From the results shown in Table 6, the CO 2 facilitated transport film of the water-based gel film has a CO 2 carrier It can be seen that the CO 2 separation performance for the feed gas FG that does not contain water vapor cannot be fully demonstrated regardless of the presence or absence of water vapor.
  • Comparative Example 7 is a sample in which no CO2 carrier was added to the gel film of Example 4. From the results shown in Table 6, the presence of an organic solvent in the gel film caused dissolution without the CO2 carrier. ⁇ Although the CO 2 separation performance in the diffusion mechanism is also reduced to about one-sixth of the CO 2 separation performance in the CO 2 facilitated transport mechanism, compared to Comparative Examples 1 to 6, the feed gas FG that does not contain water vapor On the other hand, it shows high CO 2 separation performance. From this, it is inferred that both the permeation resistance to the reaction product of carbon dioxide and the CO2 carrier and the permeation resistance to carbon dioxide are lower in the organic solvent than in water.
  • Examples 10 to 12, 15 to 21, Examples 1A to 1D, and Examples 2A to 2B are all samples in which an organic solvent is predominantly present in the gel film and water is also partially included.
  • Table 5 as membrane performance, CO 2 permeance: 3.1 ⁇ 10 -6 to 12 ⁇ 10 -6 [mol/(m 2 ⁇ s ⁇ kPa)], N 2 permeance: 1.8 ⁇ 10 ⁇ 8 ⁇ 5.1 ⁇ 10 ⁇ 8 [mol/(m 2 ⁇ s ⁇ kPa)] and CO 2 /N 2 selectivity: 98-410 are obtained.
  • organic solvent predominately exists in the gel film, and therefore, as in the samples of Examples 1 to 9, even without water vapor added in the feed gas FG, CO2 - facilitated transport It can be seen that the mechanism exhibits good CO 2 separation performance.
  • FIG. 2 is a graph showing the relationship between CO 2 permeance and water content Xm in Examples 1, 1A to 1D and the relationship between CO 2 permeance and water content Xm in Examples 2, 2A to 2B. shown in a simplified form.
  • the vertical axis is the CO 2 permeance
  • the horizontal axis is the water content Xm (% by weight) based on the total weight of the water-containing mixed solvent.
  • the CO 2 permeance of Examples 1A to 1D increased from 4.2 wt %, 6.3 wt %, 10 wt %, and 17 wt %, and the CO 2 It can be seen that the CO 2 permeance varies from +10%, +20%, -14%, ⁇ 0% with respect to the permeance. From this, if the content Xm is at least about 20% by weight or less, the effect of the dominant presence of the organic solvent in the gel film appears significantly, and even if water vapor is not added to the feed gas FG, , it can be seen that good CO 2 separation performance by the CO 2 facilitated transport mechanism is exhibited.
  • the CO 2 permeance of Examples 2A to 2B is lower than the CO 2 permeance of Example 2 as the content Xm increases from 4.3% by weight to 11% by weight. increases by +17% and +33%. From this, if the content Xm is at least about 20% by weight or less, the effect of the dominant presence of the organic solvent in the gel film is significant without being inhibited by the presence of water in the gel film. , and it can be seen that good CO 2 separation performance by the CO 2 facilitated transport mechanism is exhibited even if water vapor is not added to the feed gas FG.
  • the water content Xm of each of the samples of Examples 1 to 9, 13, and 14 was 0%.
  • the gel films of Examples 1 and 2 contained a small amount of water and the content Xm was about 1 to 2%, the CO 2 permeance and the content Xm shown in FIG. From the relationship, when the content Xm of the gel film containing no minute amount of water is 0%, the effect of the dominant presence of the organic solvent in the gel film is lost or greatly reduced. Not likely.
  • the CO 2 carrier is dissolved in an organic solvent such as an alkali metal carbonate to ionize metal ions.
  • an organic solvent such as an alkali metal carbonate to ionize metal ions.
  • the metal ion M + of the alkali metal is surrounded by the organic solvent molecules such that the charge-localized ⁇ - of the organic solvent molecule faces the metal ion M + . It is thought that it is in a solvated state.
  • the CO 2 carrier is an amine-based carrier.
  • the CO 2 carrier is an amine-based carrier.
  • the charge-localized carbon dioxide molecules becomes an amine (RNH It is thought that it dissolves in an organic solvent by forming a hydrogen bond facing the H atom of 2 ).
  • the CO 2 carrier is an alkali metal carbonate or the like or an amine
  • it is taken into an organic solvent to form a carbon dioxide molecule and a metal ion M + or a carbon dioxide molecule and an amine (Chemical 3).
  • the bond shown in (Chemical 4) is formed and they move together in the gel film, the metal ion M + and the amine can be transported by CO2 - facilitated transport even in the absence of water in the gel film. serve as a carrier for
  • the CO 2 partial pressure and the N 2 partial pressure in the first space 3 were adjusted to 5 kPa and 105 kPa, respectively.
  • the pressure of the second space 4 was fixed at 100 kPa (atmospheric pressure), and the total pressure of the feed gas FG (feed pressure and Abbreviated name, the pressure of the first space 3) is increased in three stages from 110 kPa to 150 kPa, 200 kPa, and 250 kPa, and the CO2 partial pressure is increased from 5 kPa to about 6.8 kPa, about 9.1 kPa, and about 11 kPa, The CO2 permeance and N2 permeance were measured and the CO2 / N2 selectivity was calculated.
  • FIG. 3 graphically shows the relationship between the CO 2 permeance and the CO 2 partial pressure in Examples 4 and 5, respectively.
  • FIG. 4 graphically shows the relationship between the N2 permeance and the N2 partial pressure for Examples 4 and 5, respectively. 3 and 4, the vertical axis is CO2 permeance or N2 permeance, and the horizontal axis is CO2 partial pressure or N2 partial pressure.
  • the first space 3 and the second space 4 was set to be 10 kPa or more, and the minimum value of the CO2 partial pressure was 5 kPa.
  • the CO2 partial pressure is about 4.5 kPa. It is estimated that about 10% higher CO 2 permeance can be obtained. Therefore, from the results of FIG. 3, even when the pressure difference between the first space 3 and the second space 4 is 0 kPa to 150 kPa and no water vapor is added to the feed gas FG, good CO 2 It can be seen that separation performance is exhibited.
  • the total pressure of the feed gas FG is 110 kPa and the flow rates of CO2 and N2 are 2.4 mL/min and 2400 mL/min.
  • the CO2 partial pressure is about 0.11 kPa.
  • Ar gas was used as the sweep gas SG and supplied to the second space 4 at a flow rate of 10 mL/min. Also, the pressure on the side of the second space 4 is the atmospheric pressure (0 kPa (G), 100 kPa).
  • the flow rate of He when the feed gas FG is a mixed gas of CO 2 and He is 2400 mL/min, which is the same as the flow rate of N 2 .
  • the temperature (operating temperature) of the feed gas FG was set to 30° C. as in Evaluations 1 and 2, and the feed gas FG contained no moisture.
  • the purpose of using a mixed gas of CO2 and He as the feed gas FG is that the N2 permeance when using a mixed gas of CO2 and N2 was below the detection limit (UL), so it was dissolved from N2 . ⁇ The permeance of the main component gas was confirmed using He, which easily permeates through the diffusion mechanism.
  • Comparative Example 1 the relative humidity was varied from 0% to 80% in 20% increments, and for Example 11, the relative humidity was varied from 0% to 50% in 10% increments. 2 permeance and N 2 permeance were measured and the CO 2 /N 2 selectivity was calculated. Table 12 shows the measurement results and calculation results of Comparative Example 1, and Table 13 shows the measurement results and calculation results of Example 11. 5 graphically shows the relationship between CO 2 permeance and relative humidity in Comparative Example 1, and FIG. 6 graphically shows the relationship between CO 2 permeance and relative humidity in Example 11. As shown in FIG. In FIG. 5, the CO2 permeance below the limit of detection (UL) in Table 12 is labeled as zero.
  • UL limit of detection
  • Example 11 water vapor was added to the feed gas FG as the relative humidity was increased from 0% to 10%, 20%, 30%, and 40%. It can be seen that the CO 2 permeance varies from ⁇ 6.5%, ⁇ 0%, +2.2%, +8.7%, +8.7% to the CO 2 permeance at 0% relative humidity without any relative humidity.
  • a mixed gas containing a predetermined main component gas and CO 2 is supplied as a gas to be treated to the facilitated transport membrane, and CO 2 that has permeated the facilitated transport membrane is separated from the gas to be treated.
  • Characterized CO2 separation method a mixed gas containing a predetermined main component gas and CO 2 is supplied as a gas to be treated to the facilitated transport membrane, and CO 2 that has permeated the facilitated transport membrane is separated from the gas to be treated.
  • the main component gas of the target gas to be treated for CO 2 separation 1 such as N 2 , O 2 , H 2 , and CH 4 that permeate the CO 2 facilitated transport membrane only by the dissolution/diffusion mechanism.
  • the gas to be treated corresponds to the feed gas FG used in the evaluation experiment of the membrane performance of the facilitated transport membrane described above, but is not limited to a mixed gas of N 2 and CO 2 .
  • the CO 2 concentration in the gas to be treated is assumed to be within a range including about 4.5 mol % in evaluations 1, 2 and 4 described above and about 0.1 mol % in evaluation 3. Therefore, the concentration of CO 2 in the gas to be treated by this separation method is assumed to be from about 0.1 mol % to about 4.5 mol % as one of the suitable target ranges. Furthermore, in Evaluation 2, good CO 2 separation performance was exhibited even when the CO 2 partial pressure exceeded 11 kPa, so this CO 2 partial pressure was adjusted to the CO 2 partial pressure when the total pressure of the feed gas FG was 110 kPa or 100 kPa. When converted to concentration, it is about 10 mol % or about 11 mol %.
  • another preferred target range for the CO 2 concentration in the gas to be treated in the present separation method is from about 4.5 mol % to about 11 mol %.
  • this separation method may be applied to a gas to be treated having a CO 2 concentration of less than 0.1 mol % or more than 11 mol %.
  • CO 2 facilitated transport membrane of the conventional water-based gel membrane can not be processed.
  • a major feature is that carbon dioxide can be separated even from gas to be treated that does not contain any moisture.
  • this separation method does not exclude the case where the gas to be treated contains moisture , and the relative humidity range (e.g., 40% or 50% or less), carbon dioxide can be separated from the gas to be treated by using this separation method.
  • the temperature (operating temperature) of the gas to be treated supplied to the facilitated transport membrane 10 ° C. including the operating temperature of 30 ° C. in the membrane performance evaluation experiment of the facilitated transport membrane
  • a temperature range of ⁇ 50° C. and ⁇ 50° C. is assumed.
  • the present facilitated transport film is not greatly affected by the water content Xm in the gel film and the water content in the gas to be treated, because the organic solvent is predominantly present in the gel film. 2 Separation performance can be fully exhibited.
  • the CO 2 separation performance is greatly affected by the water content in the water-based gel membrane.
  • the amount of water in the water-based gel film is greatly affected by the change in operating temperature, but this facilitated transport film, which basically does not contain water in the gel film, is considered to be less affected by the change in operating temperature.
  • the operating temperature was only one point of 30 ° C., but if the temperature range is 10 ° C. or higher and 50 ° C. or lower, the gas to be treated that does not contain moisture It is thought that the present facilitated transport membrane can exhibit the unique effect of being able to separate CO 2 from .
  • the organic solvent with the lowest boiling point among the specific examples listed as candidates for the organic solvent constituting the facilitated transport film is acetone, whose boiling point is 56°C. is. Therefore, within the temperature range of 10° C. or higher and 50° C. or lower, the gel of the facilitated transport film can be used as long as the organic solvent selected from the first to fourth candidate groups and having a boiling point of 56° C. or higher is used. Evaporation of the organic solvent from the membrane can be suppressed. From the viewpoint of suppressing evaporation of the organic solvent from the gel film, it is preferable to use an organic solvent having a higher boiling point.
  • CO 2 separation apparatuses 10 and 20 schematically shown in FIGS. 7 and 8 are used.
  • the CO 2 separation devices 10 and 20 have the facilitated transport membranes 11 and 21 mounted inside the housing, and the first spaces 12 and 22 and the second spaces 13 and 23 separated by the facilitated transport membrane 10 inside the housing. Prepare.
  • the first space 12 of the CO 2 separation device 10 has a first inlet 14 for feeding the gas to be treated as a feed gas FG into the first space 12, and the facilitated transport membrane 11.
  • a first discharge port 15 is provided for discharging the post-processed feed gas EG that has not permeated from the first space 12 .
  • the second space 13 of the CO 2 separation device 10 has a second inlet 16 for introducing the sweep gas SG into the second space 13, and a permeate gas PG that has permeated the facilitated transport membrane 11 and the sweep gas SG.
  • a second discharge port 17 is provided for discharging the mixed exhaust gas MG from the second space 13 .
  • the first space 22 of the CO 2 separation device 20 has a first inlet 24 for feeding the gas to be treated as feed gas FG into the first space 22 and the facilitated transport membrane 21.
  • a first discharge port 25 is provided for discharging the post-processed feed gas EG that has not permeated from the first space 22 .
  • the second space 23 of the CO 2 separation device 20 is not provided with a second inlet, and the permeated gas PG containing CO 2 that has permeated the facilitated transport membrane 21 is discharged from the second space 23 as the discharged gas MG. Only the second outlet 27 is provided.
  • the CO 2 separation device 10 corresponds to the flow-type gas permeation cell 2 used in the evaluation experiment of the membrane performance of the facilitated transport membrane described above, and the gas to be treated is fed by the sweep gas method. It is used in this separation method in which carbon dioxide is separated by introducing as In the case of the sweep gas method, in order to generate a CO 2 partial pressure difference between the first space 12 and the second space 13, which is the driving force for CO 2 permeation, the permeated gas PG that has permeated the facilitated transport membrane 11 is A sweep gas SG containing no carbon dioxide is supplied into the second space 13 so that the CO 2 partial pressure in the space 13 is low.
  • the gas type of the sweep gas SG depends on the utilization form of the process target gas EG discharged from the first discharge port 15 and the utilization form of the permeation gas PG contained in the exhaust gas MG discharged from the second discharge port 17. and use the appropriate gas species. Therefore, the gas type of the sweep gas SG is not limited to the Ar gas used in the evaluation experiment of the film performance of the facilitated transport film described above.
  • the pressure difference between the first space 12 and the second space 13 is in the range of 0 kPa to 150 kPa, as discussed in Evaluation 2 above, and water vapor is added to the feed gas FG. It is clear that good CO2 separation performance by the CO2 - facilitated transport mechanism is exhibited even if the CO2-facilitated transport mechanism is not used.
  • the CO 2 separator 20 is used in this separation method in which a gas to be treated is introduced as a feed gas FG by a depressurization method to separate carbon dioxide.
  • a depressurization method in order to generate a CO2 partial pressure difference between the first space 22 and the second space 23, which is the driving force for CO2 permeation, the pressure in the second space 23 (permeation side pressure) is reduced to the first
  • the pressure in the space 22 is made lower than the pressure on the supply side.
  • the CO2 partial pressure in the first space 22 is within the preferred range of about 0.11 kPa to about 11 kPa, with no added water vapor in the feed gas FG. It is also clear that good CO 2 separation performance is exhibited by the CO 2 facilitated transport mechanism. Therefore, even in the present separation method by the reduced pressure method, the CO 2 partial pressure difference within the preferred range of the CO 2 partial pressure difference between the first space 12 and the second space 13 obtained in the present separation method by the sweep gas method is obtained.
  • the permeate-side pressure in the second space 23 is made lower than the supply-side pressure in the first space 22 .
  • the supply side pressure is atmospheric pressure (100 kPa)
  • the permeate side pressure is reduced, for example, within the range of 1 kPa or more and less than 100 kPa so as to obtain a desired CO 2 partial pressure difference.
  • the first space 22 side may be pressurized.
  • CO and CH4 are generated by a reduction reaction from the CO2 contained in the exhaust gas MG by the CO2 reduction catalyst.
  • CO2 contained in the exhaust gas MG can be chemically absorbed , chemically CO 2 immobilization treatment, etc., in which CO 2 is immobilized by the action of adsorption, physical adsorption, etc., are envisioned.
  • the CO 2 separation devices 10 and 20 may be used not only when used singly, but also when a plurality of devices are connected in series, in parallel, or in series-parallel.
  • the first outlets 15, 25 of the CO 2 separation devices 10, 20 in the preceding stage and the first inlets 14, 24 of the CO 2 separation devices 10, 20 in the subsequent stage are connected to form the first
  • the post-treatment feed gas EG discharged from the first space 12, 22 is fed into the post-stage first space 12, 22 as the post-treatment target gas as the feed gas FG.
  • the facilitated transport membranes 11 and 21 are flat CO 2 facilitated transport membranes, but the shape of the facilitated transport membranes 11 and 21 is As with conventional CO 2 -facilitated transport membranes of water-based gel membranes, membranes of arbitrary shapes such as flat plates and cylinders can be used.
  • the mixing ratio of each component, the film thickness of the gel film, etc. in the composition of the facilitated transport film (polymer compound, organic solvent, CO2 carrier, and water (if included)) exemplified in the above embodiment are the same as those of the present invention are examples for ease of understanding, and the present invention is not limited to CO2- facilitated transport membranes with those values.
  • each of the polymer compound, the organic solvent, and the CO 2 carrier may be used in any combination of two or more as long as the effect unique to the present invention exerted by the facilitated transport film is not impaired.
  • the production method described in the above embodiment comprises the steps of preparing a gel-like mixture containing an organic solvent, a polymer compound, and a CO 2 carrier, and coating the gel-like mixture on the surface of a porous membrane that is a support to obtain a gel.
  • a gel-like mixture containing an organic solvent, a polymer compound, and a CO 2 carrier
  • Various variations are possible as long as they comprise the two basic steps of the process of fabricating the membrane and include the organic solvent, the polymer and the CO2 carrier in the fabricated gel membrane.
  • the CO 2 carrier is added in step 2 to the intermediate gel prepared in step 1, and the organic solvent and high A gel-like mixture of molecular compound and CO2 carrier was prepared.
  • the CO 2 carrier may be added during the preparation of the homogeneous intermediate gel of step 1 to prepare the gel mixture in step 1 without going through step 2.
  • the timing of adding purified water is after preparing the mixed solution of the organic solvent and the polymer compound in step 1.
  • a mixed solvent of the organic solvent and water may be prepared in advance by adding to the organic solvent at the same time as the mixed solution of the organic solvent and the polymer compound is prepared, or before preparing the mixed solution. , in step 2, may be added at the same time as the CO 2 carrier is added to the intermediate gel.
  • the stirring time required for preparing the intermediate gel-like material and the gel-like mixture is exemplified, but the stirring time is an example, and the organic solvent, polymer compound, and CO 2 carrier used are It can be changed as appropriate according to the amount and the like.
  • the CO 2 -facilitated transport membrane according to the present invention can be used for separating carbon dioxide (CO 2 ). Available to separate carbon.

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Abstract

L'invention concerne une membrane de transport facilité par CO2 qui est dotée d'une membrane de gel comprenant un composé polymère et un solvant organique, dans laquelle un transporteur de CO2 est contenu dans la membrane de gel, l'apport d'eau depuis l'extérieur, qui est nécessaire pour les membranes de transport facilité par CO2 conventionnelles, n'étant pas nécessaire pour la membrane de transport facilité par CO2 selon l'invention ou pouvant être considérablement réduit. Le solvant organique est de préférence choisi parmi un solvant organique à base d'alcool et un solvant organique aprotique. Le composé polymère est de préférence choisi parmi des composants polymères synthétiques appartenant à un premier groupe candidat incluant l'alcool polyvinylique, l'acétate de vinyle, le polypropylène glycol, l'acide polyacrylique et le polyéthylène glycol, des composants polymères naturels appartenant à un deuxième groupe candidat incluant la pectine, le chitosane, l'agarose, la pâte d'amidon, la gomme xanthane, la gomme gellane et l'acide alginique, et des composants polymères semi-synthétiques appartenant à un troisième groupe candidat incluant la carboxyméthylcellulose et l'hydroxypropylcellulose.
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