WO2017135230A1 - Membrane de séparation de dioxyde de carbone et son procédé de production - Google Patents

Membrane de séparation de dioxyde de carbone et son procédé de production Download PDF

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WO2017135230A1
WO2017135230A1 PCT/JP2017/003341 JP2017003341W WO2017135230A1 WO 2017135230 A1 WO2017135230 A1 WO 2017135230A1 JP 2017003341 W JP2017003341 W JP 2017003341W WO 2017135230 A1 WO2017135230 A1 WO 2017135230A1
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carbon dioxide
layer
separation membrane
alkali metal
carrier
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English (en)
Japanese (ja)
Inventor
直道 木村
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MOLECULAR GATE MEMBRANE MODULE TECHNOLOGY RESEARCH ASSOCIATION
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MOLECULAR GATE MEMBRANE MODULE TECHNOLOGY RESEARCH ASSOCIATION
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    • 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
    • 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
    • B01D69/1071—Woven, non-woven or net mesh
    • 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
    • B01D69/1214—Chemically bonded layers, e.g. cross-linking
    • 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
    • B01D71/38—Polyalkenylalcohols; Polyalkenylesters; Polyalkenylethers; Polyalkenylaldehydes; Polyalkenylketones; Polyalkenylacetals; Polyalkenylketals
    • B01D71/381—Polyvinylalcohol
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • 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 carbon dioxide separation membrane for separating carbon dioxide from a mixed gas containing carbon dioxide, and a method for producing the same.
  • Patent Document 1 discloses a gas separation membrane for separating at least one acidic gas from a gas mixture, A porous first layer; Alkali metal hydroxide, alkali metal alkoxide, alkali metal carbonate, alkali metal bicarbonate, alkali metal phosphate, alkaline earth metal hydroxide, alkaline earth metal alkoxide, alkaline earth metal carbonate At least one acidic gas carrier having a molecular weight of 150,000 or less selected from a salt, an alkaline earth metal bicarbonate, an alkali metal phosphate, an organic amine, an ionic liquid, and a metal complex; and polyethylene glycol, polypropylene glycol A second layer which is a separation active layer containing a hydrophilic crosslinked polymer having at least one repeating unit selected from polyvinyl alcohol, polyvinyl acetate, polyvinyl pyrrolidone, polyethyleneimine and polyallylamine; There is disclosed a gas separation membrane comprising a specific crosslinked polymer and
  • Patent Document 2 discloses a gas separation membrane characterized by having a separation active membrane containing a specific diamine compound having a boiling point or decomposition temperature of 200 ° C. or higher and a crosslinked polymer having a specific repeating unit, Is disclosed.
  • Patent Document 3 discloses a hydrophobic porous film having heat resistance of 100 ° C. or higher, Formed on the surface of the porous membrane, comprising at least one carbon dioxide carrier selected from the group consisting of alkali metal carbonates, alkali metal bicarbonates and alkali metal hydroxides and moisture, and the following (A) A polymer compound layer having a crosslink structure including a hydrolysis-resistant bond selected from the following group (B), formed by a single crosslinkable group selected from the group; A carbon dioxide separation member that selectively allows carbon dioxide gas to permeate from a mixture of carbon dioxide gas and hydrogen gas under a temperature condition of 100 ° C. to 250 ° C. is disclosed.
  • a carbon dioxide separation member that selectively allows carbon dioxide gas to permeate from a mixture of carbon dioxide gas and hydrogen gas under a temperature condition of 100 ° C. to 250 ° C. is disclosed.
  • (A) group —OH, —NH 2 , —Cl, —CN, —COOH, epoxy group
  • a CO 2 facilitated transport membrane having CO 2 / H 2 selectivity performance at a temperature of above 100 ° C. A gel layer comprising an additive made of cesium carbonate, cesium bicarbonate or cesium hydroxide in a gel film containing moisture is supported on a hydrophilic porous film having heat resistance of 100 ° C. or higher.
  • a CO 2 facilitated transport membrane is disclosed.
  • Patent Document 5 includes a separation functional layer containing a specific amine compound as a high molecular polymer and a hydrophobic layer laminated on both sides of the separation functional layer, A separation membrane in which the separation functional layer contains a crack inhibitor is disclosed.
  • Patent Document 6 discloses a gas separation membrane comprising a resin composition containing an alkali metal compound (A) and a vinyl alcohol copolymer (B) containing a cationic group, Is disclosed.
  • Patent Document 7 is characterized by comprising a resin composition containing an alkali metal compound (A) and a vinyl alcohol copolymer (B) having a sulfonate group and / or a sulfonic acid group.
  • a gas separation membrane is disclosed.
  • Patent Document 8 includes a resin composition containing a vinyl alcohol polymer (A), an ionic polymer (B) containing a cation and / or an anion, and an alkali metal compound (C).
  • a gas separation membrane characterized by the above is disclosed.
  • a conventional separation membrane has a function of selectively separating carbon dioxide from a mixed gas containing carbon dioxide, but is not satisfactory with respect to the permeation rate and selective permeability of carbon dioxide.
  • development of a highly functional carbon dioxide separation membrane has been desired.
  • An object of the present invention is to provide a carbon dioxide separation membrane excellent in carbon dioxide permeation rate and selective permeability, and a method for producing the same.
  • the present invention is a carbon dioxide separation membrane having a separation functional layer on a porous support layer
  • the separation functional layer includes a hydrophilic polymer layer and a carrier layer
  • the hydrophilic polymer layer includes at least a polyvinyl alcohol-based polymer
  • the carrier layer includes at least one carrier substance selected from the group consisting of alkali metal carbonates, alkali metal bicarbonates, alkali metal hydroxides, amino acids and amine compounds, and a group consisting of acids and acid salts.
  • the present invention relates to a carbon dioxide separation membrane comprising at least one selected reaction promoting substance.
  • the present inventor divides the separation functional layer, which is essentially a layer having a function of separating carbon dioxide, into at least two layers of a hydrophilic polymer layer and a carrier layer to increase the concentration of the carrier substance in the carrier layer.
  • a carbon dioxide separation membrane excellent in carbon dioxide permeation rate and selective permeability can be obtained by adding a reaction promoting substance that promotes the reaction between carbon dioxide and the carrier substance into the carrier layer.
  • the acid is preferably boric acid from the viewpoint that the reaction promoting effect and the function of crosslinking the polyvinyl alcohol polymer are excellent.
  • the polyvinyl alcohol polymer of the hydrophilic polymer layer is preferably crosslinked at least at the interface with the carrier layer by reaction with the reaction promoting substance.
  • the carbon dioxide separation membrane of the present invention preferably has a protective layer on the separation functional layer.
  • the present invention also relates to a carbon dioxide separation membrane module including the carbon dioxide separation membrane.
  • the present invention provides, on the porous support layer, at least one carrier material selected from the group consisting of alkali metal carbonates, alkali metal bicarbonates, alkali metal hydroxides, amino acids and amine compounds, Applying a carrier layer forming solution containing at least one reaction accelerator selected from the group consisting of an acid and an acid salt and curing to form a carrier layer; It is related with the manufacturing method of the said carbon dioxide separation membrane including the process of apply
  • a hydrophilic polymer layer having a uniform thickness and no defects can be formed by forming the hydrophilic polymer layer on the carrier layer.
  • the carbon dioxide separation membrane of the present invention has a multilayer structure in which the separation functional layer includes a hydrophilic polymer layer and a carrier layer. Excellent permselectivity.
  • the carbon dioxide separation membrane of the present invention is a carbon dioxide separation membrane having a separation functional layer on a porous support layer,
  • the separation functional layer includes a hydrophilic polymer layer and a carrier layer,
  • the hydrophilic polymer layer includes at least a polyvinyl alcohol-based polymer,
  • the carrier layer includes at least one carrier substance selected from the group consisting of alkali metal carbonates, alkali metal bicarbonates, alkali metal hydroxides, amino acids and amine compounds, and a group consisting of acids and acid salts. And at least one selected reaction accelerator.
  • porous support layer As the porous support layer, those known in the art can be used without particular limitation.
  • the porous support layer can be produced using, for example, a polymer described later, and ceramics or polyethylene terephthalate (PET) film can also be used.
  • a polymer when producing using a polymer, after dissolving the polymer in a solvent to obtain a raw material solution, the raw material solution is brought into contact with a coagulation liquid (a mixed solution of a solvent and a non-solvent),
  • a porous support layer can be produced by a method of inducing phase separation by increasing the non-solvent concentration (non-solvent-induced phase separation method; NIPS method, see Japanese Patent Publication No. 1-2003).
  • the ceramic include alumina, zirconia, titania, and silica.
  • polysulfone examples include polysulfone (PSF), polyethersulfone, polyarylethersulfone, polyphenylenesulfone, triacetylcellulose, cellulose acetate, polyacrylonitrile, polyvinylidene fluoride, aromatic nylon, and polyethylene.
  • PSF polysulfone
  • polyethersulfone examples include polyethersulfone, polyarylethersulfone, polyphenylenesulfone, triacetylcellulose, cellulose acetate, polyacrylonitrile, polyvinylidene fluoride, aromatic nylon, and polyethylene.
  • PET terephthalate
  • PET polyethylene naphthalate
  • polyarylate polyarylate
  • polyimide polyimide
  • epoxy resin examples of the polysulfone, polyarylethersulfone, and epoxy resin are preferably used from the viewpoint of being chemically and mechanically stable.
  • the solvent is not particularly limited as long as it is soluble in the coagulation liquid, and examples thereof include N-methylpyrrolidone (NMP), acetone, and dimethylformamide.
  • NMP N-methylpyrrolidone
  • examples of the non-solvent include water, monohydric alcohol, polyhydric alcohol, ethylene glycol, and tetraethylene glycol.
  • a swelling agent to increase the number of through-holes in the support layer after solidification and improve gas permeability.
  • the swelling agent include polyethylene glycol, polyvinyl pyrrolidone, hydroxypropyl cellulose, sodium chloride, lithium chloride, and magnesium bromide. These may be used alone or in combination of two or more.
  • these swelling agents polyethylene glycol is preferable, and polyethylene glycol having a weight average molecular weight of 400 to 800 is particularly preferable.
  • the method for contacting the raw material solution and the coagulating liquid is not particularly limited, and examples thereof include a method of immersing the raw material solution in the coagulating liquid.
  • the concentration of the solvent in the coagulating liquid is not particularly limited, but in the coagulation of the raw material solution, changing the solvent concentration in the coagulating liquid changes the structure of the support film and can increase the pressure resistance.
  • the pore diameter of the pores of the porous support layer is preferably 200 nm or less, more preferably 100 nm or less.
  • the thickness of the porous support layer is not particularly limited as long as the gas permeability of the porous support layer is larger than the gas permeability of the separation functional layer, but it is usually about 25 to 125 ⁇ m, preferably 40 to 75 ⁇ m.
  • UF membrane ultrafiltration membrane
  • a woven fabric or a non-woven fabric may be laminated on the porous support layer.
  • the separation functional layer includes a hydrophilic polymer layer and a carrier layer.
  • the carrier layer is selected from the group consisting of at least one carrier substance selected from the group consisting of alkali metal carbonates, alkali metal bicarbonates, alkali metal hydroxides, amino acids and amine compounds, and acids and acid salts. And at least one reaction accelerator.
  • Examples of the alkali metal carbonate include lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, and cesium carbonate.
  • Examples of the alkali metal bicarbonate include lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, rubidium hydrogen carbonate, and cesium hydrogen carbonate.
  • Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide. Among these, from the viewpoint of good affinity with carbon dioxide, a compound containing potassium, rubidium, and cesium as an alkali metal element is preferable, and cesium is particularly preferable.
  • amino acids include glycine, alanine, serine, proline, hydroxyproline, arginine, dimethylaminoglycine, 2,3-diaminopropionic acid, and salts thereof.
  • amine compound include alkanolamine (monoethanolamine, diethanolamine, triethanolamine, ethyl monoethanolamine, n-butylmonoethanolamine, dimethylethanolamine, ethyldiethanolamine, n-butylethanolamine, di-n-butyl.
  • the acid and acid salt examples include oxo acids such as boric acid, arsenous acid, telluric acid, selenious acid, and salts thereof.
  • oxo acids such as boric acid, arsenous acid, telluric acid, selenious acid, and salts thereof.
  • boric acid or a borate from the viewpoint that the reaction promoting effect and the function of crosslinking the polyvinyl alcohol polymer are excellent.
  • the reaction promoting substance is preferably added in an amount of 0.005 to 0.2 mol, more preferably 0.01 to 0.1 mol, with respect to 1 mol of the carrier substance.
  • the addition amount of the reaction accelerator is less than 0.005 mol, it becomes difficult to improve the permeation rate and selective permeability of carbon dioxide, or the crosslinking of the polyvinyl alcohol polymer in the hydrophilic polymer layer becomes insufficient. There is a tendency.
  • the amount exceeds 0.2 mol the water content of the hydrophilic polymer layer decreases due to an increase in the crosslinking density, and the CO 2 permeation rate tends to decrease.
  • the method for forming the carrier layer is not particularly limited, and examples thereof include a method in which a carrier layer forming solution containing a carrier substance and a reaction promoting substance is applied on the porous support layer and cured.
  • the coating method is not particularly limited, but for example, spin coating method, bar coating, die coating coating, blade coating, air knife coating, gravure coating, roll coating coating, spray coating, dip coating, comma roll method, kiss coating method, screen printing, and Ink jet printing and the like can be mentioned.
  • the solvent is not particularly limited as long as it can dissolve the carrier substance and the reaction promoting substance.
  • the solid content concentration of the carrier layer forming solution is usually about 5 to 40% by weight, preferably 10 to 30% by weight.
  • the carrier layer may contain, in addition to the carrier substance and the reaction promoting substance, known carrier substances, polymers, additives and the like as long as the effects of the present invention are not impaired.
  • the thickness of the carrier layer is not particularly limited, but is usually 1 to 20 ⁇ m, preferably 3 to 10 ⁇ m.
  • the hydrophilic polymer layer contains at least a polyvinyl alcohol polymer.
  • the polyvinyl alcohol polymer is a polymer having a polyvinyl alcohol structure in the molecule, and may be a homopolymer or a copolymer.
  • the polyvinyl alcohol polymer may be modified with a carboxy group, an amino group, an epoxy group, or the like.
  • the weight average molecular weight of the polyvinyl alcohol polymer is not particularly limited, but is usually about 5,000 to 1,000,000, preferably 40,000 to 400,000.
  • the degree of saponification of the polyvinyl alcohol polymer is preferably 90 mol or more, more preferably 95 mol or more.
  • the hydrophilic polymer layer is made of polyethylene alcohol, polyethylene glycol di (meth) acrylate, polypropylene glycol, polypropylene glycol di (meth) acrylate, polyethyleneimine, polyallylamine, polyamide epichlorohydrin, polyacrylic as well as polyvinyl alcohol polymer.
  • One or more hydrophilic polymers such as acid, polymethacrylic acid, polyvinylpyrrolidone, polyacrylamide, polyvinylamine, polyornithine, and polylysine may be included.
  • the polyvinyl alcohol polymer is preferably used in an amount of 20% by weight or more, more preferably 40% by weight or more.
  • the method for forming the hydrophilic polymer layer is not particularly limited, and examples thereof include a method in which a hydrophilic polymer layer forming solution containing at least a polyvinyl alcohol-based polymer is applied on the carrier layer and cured.
  • the coating method is not particularly limited, but for example, spin coating method, bar coating, die coating coating, blade coating, air knife coating, gravure coating, roll coating coating, spray coating, dip coating, comma roll method, kiss coating method, screen printing, and Ink jet printing and the like can be mentioned.
  • the solvent is not particularly limited as long as it can dissolve the polyvinyl alcohol polymer.
  • water, methanol, ethanol, isopropyl alcohol, chloroform, methylene chloride, acetone, dioxane, methyl acetate, cyclohexanone, methyl ethyl ketone, acetonitrile, tetrachloroethylene examples include tetrahydrofuran, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. These may be used alone or in combination of two or more.
  • the solid content concentration of the hydrophilic polymer layer forming solution is usually about 1 to 10% by weight, preferably 2 to 6% by weight.
  • the polyvinyl alcohol polymer of the hydrophilic polymer layer is cross-linked by reaction with a reaction promoting substance added to the carrier layer at least at the interface with the carrier layer.
  • a reaction promoting substance added to the carrier layer at least at the interface with the carrier layer.
  • the polyvinyl alcohol-based polymer may be crosslinked throughout the layer, but is preferably crosslinked only at the interface with the carrier layer because the carbon dioxide permeability decreases due to crosslinking.
  • the hydrophilic polymer layer may contain, in addition to the polymer, known crosslinking agents and additives as long as the effects of the present invention are not impaired.
  • the thickness of the hydrophilic polymer layer is not particularly limited, but is usually 0.5 to 10 ⁇ m, preferably 2 to 8 ⁇ m.
  • the carbon dioxide separation membrane of the present invention preferably has a protective layer on the separation functional layer.
  • the protective layer is provided in order to impart flexibility and mechanical strength to the separation membrane or to improve workability (for example, winding property) when producing the separation membrane module.
  • the material for forming the protective layer is not particularly limited, and examples thereof include polyalkylene glycol, polysiloxane, polyester, fluororesin, and polyolefin. It is particularly preferable to use polysiloxane.
  • the method for forming the protective layer is not particularly limited, and a known method can be employed.
  • the thickness of the protective layer is not particularly limited, but is preferably 0.5 to 20 ⁇ m in order to sufficiently impart the function to the separation membrane and to suppress a decrease in gas permeability of the separation membrane.
  • the thickness is preferably 1 to 10 ⁇ m.
  • the carbon dioxide separation membrane module of the present invention includes the separation membrane.
  • the type of the carbon dioxide separation membrane module is not particularly limited, and examples thereof include a flat membrane type, a spiral type, a pleat type, and a bowl type.
  • the carbon dioxide separation membrane and carbon dioxide separation membrane module of the present invention can selectively and efficiently separate carbon dioxide from a mixed gas containing carbon dioxide and hydrogen, for example.
  • a gas permeation measuring device manufactured by GL Sciences Inc. was used.
  • a mixed gas containing CO 2 gas (80% by volume) and He gas (20% by volume) is supplied to the supply side of the produced carbon dioxide separation membrane at atmospheric pressure or a total pressure of 0.7 MPa, and the permeation side at atmospheric pressure.
  • a humidified Ar gas having a certain humidity of 90% was circulated.
  • a part of the Ar gas on the permeate side was introduced into the gas chromatograph at regular time intervals, and the permeance of CO 2 and He was determined from the increase in the concentration of CO 2 gas and He gas over time.
  • the mixed gas was humidified to 90% humidity using a bubbler. Measurement was performed 15 hours after supplying the mixed gas.
  • the setting conditions of the gas permeation measuring device, the analysis conditions of the gas chromatography, and the calculation method of the gas permeance are as follows.
  • N CO2 and N He are the permeation amounts of CO 2 gas and He gas
  • P f and P P are the total pressure of the feed and permeate gas
  • A is the membrane area
  • X CO 2 and X He are the CO in the feed gas.
  • Y CO2 and Y He represent the mole fraction of CO 2 gas and He gas in the permeate gas.
  • Example 1 Cesium carbonate (Wako Pure Chemical Industries, reagent grade 1) 4g, sodium polyacrylate (Wako Pure Chemical Industries, reagent special grade) 0.1g, and sodium tetraborate in an amount of 1wt% in aqueous solution Hydrate (made by Wako Pure Chemical Industries, reagent special grade) was added to pure water and dissolved to prepare a carrier layer forming solution.
  • PVA aqueous solution Kuraray, COOH modified: 30 mol%, PVA concentration: 7.4 wt%)
  • polyallylamine aqueous solution made by Kuraray, polyallylamine concentration: 51.6 wt%)
  • polyamide epichlorohydrin aqueous solution starlight
  • a hydrophilic polymer layer with a solid content concentration of 4.5 wt% solid content composition: PVA 50 wt%, polyallylamine 40 wt%, polyamide epichlorohydrin 10 wt%) mixed with PMC, polyamide epichlorohydrin concentration: 25 wt%)
  • a forming solution was prepared.
  • the carrier layer forming solution was applied on a porous support layer (NTU-3175M (UF membrane) manufactured by Nitto Denko Corporation) and dried at 60 ° C. for 1 hour to form a carrier layer. Thereafter, the hydrophilic polymer layer forming solution was applied onto the carrier layer and dried at 60 ° C. for 1 hour to form a hydrophilic polymer layer, thereby producing a carbon dioxide separation membrane.
  • NTU-3175M UF membrane
  • Examples 2 and 3 A carbon dioxide separation membrane was produced in the same manner as in Example 1 except that the formulation shown in Table 1 was changed.
  • Comparative Example 1 4 g of cesium carbonate (manufactured by Wako Pure Chemical Industries, reagent grade 1) and 0.1 g of sodium polyacrylate (manufactured by Wako Pure Chemical Industries, reagent special grade) were added to pure water and dissolved to prepare a carrier layer forming solution. .
  • a carbon dioxide separation membrane was produced in the same manner as in Example 1 except that the carrier layer forming solution was used.
  • Comparative Example 2 Mix 5 g of PVA aqueous solution (Kuraray, COOH modified: 30 mol%, PVA concentration: 5 wt%), 1.2 g of cesium carbonate (Wako Pure Chemical Industries, reagent grade 1), and 10 g of pure water until uniform. A mixed solution was obtained by stirring. To the obtained mixed solution, 0.04 g of sodium tetraborate heptahydrate (manufactured by Wako Pure Chemical Industries, Ltd., reagent grade) was added and stirred to prepare a separation functional layer forming solution. However, the separation functional layer forming solution gelled. Therefore, the separation functional layer forming solution could not be applied on the porous support layer.
  • Comparative Example 3 In Comparative Example 2, the amount of sodium tetraborate heptahydrate added was changed to 0.001 g, but the separation functional layer forming solution gelled as in Comparative Example 2. Therefore, the separation functional layer forming solution could not be applied on the porous support layer.
  • the carbon dioxide separation membrane and carbon dioxide separation membrane module of the present invention are used for separating and recovering carbon dioxide from oil field off-gas, waste incineration or thermal power generation exhaust gas, natural gas, or a mixed gas obtained by gasifying coal. It can be suitably used.

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  • 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)
  • Laminated Bodies (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

La présente invention vise à fournir : une membrane de séparation de dioxyde de carbone qui présente une excellente vitesse de perméation et une perméabilité sélective au dioxyde de carbone ; et son procédé de production. La membrane de séparation de dioxyde de carbone selon la présente invention est caractérisée en ce qu'elle comprend une couche à fonction de séparation sur une couche de support poreuse, la couche à fonction de séparation comprenant une couche de polymère hydrophile et une couche porteuse, la couche de polymère hydrophile comprenant au moins un polymère à base d'alcool polyvinylique, et la couche porteuse comprenant : au moins une substance porteuse choisie dans le groupe constitué par carbonates de métaux alcalins, bicarbonates de métaux alcalins, hydroxydes de métaux alcalins, acides aminés et composés amine ; et au moins une substance favorisant une réaction, choisie dans le groupe constitué par acides et sels d'acide.
PCT/JP2017/003341 2016-02-03 2017-01-31 Membrane de séparation de dioxyde de carbone et son procédé de production Ceased WO2017135230A1 (fr)

Applications Claiming Priority (2)

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JP2016019125A JP2017136546A (ja) 2016-02-03 2016-02-03 二酸化炭素分離膜、及びその製造方法
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JP6715575B2 (ja) * 2015-06-18 2020-07-01 住友化学株式会社 二酸化炭素分離方法及び二酸化炭素分離装置
CN107638805B (zh) * 2017-11-03 2019-11-22 宁波日新恒力科技有限公司 一种氧化石墨烯/聚乙烯醇涂层改性的反渗透膜制备方法
JP6965491B2 (ja) * 2017-11-07 2021-11-10 エルジー・ケム・リミテッド 気体分離膜の製造方法およびこれにより製造された気体分離膜
WO2020241563A1 (fr) * 2019-05-29 2020-12-03 住友化学株式会社 Composition, film de séparation de gaz et son procédé de production, et dispositif de séparation de gaz
JP2024513363A (ja) * 2021-03-31 2024-03-25 日東電工株式会社 親水性膜分離層

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US12023633B2 (en) 2017-08-21 2024-07-02 Ohio State Innovation Foundation Membranes for gas separation
CN119656897A (zh) * 2023-09-21 2025-03-21 中国科学院大连化学物理研究所 一种膜及其制备方法和在天然气膜法脱碳中的应用

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