WO2014010512A1 - Complexe de séparation de gaz acide, son procédé de fabrication et module de séparation de gaz acide - Google Patents

Complexe de séparation de gaz acide, son procédé de fabrication et module de séparation de gaz acide Download PDF

Info

Publication number
WO2014010512A1
WO2014010512A1 PCT/JP2013/068421 JP2013068421W WO2014010512A1 WO 2014010512 A1 WO2014010512 A1 WO 2014010512A1 JP 2013068421 W JP2013068421 W JP 2013068421W WO 2014010512 A1 WO2014010512 A1 WO 2014010512A1
Authority
WO
WIPO (PCT)
Prior art keywords
gas separation
acidic gas
compound
alkyl group
separation layer
Prior art date
Application number
PCT/JP2013/068421
Other languages
English (en)
Japanese (ja)
Inventor
憲一 石塚
Original Assignee
富士フイルム株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 富士フイルム株式会社 filed Critical 富士フイルム株式会社
Publication of WO2014010512A1 publication Critical patent/WO2014010512A1/fr

Links

Images

Classifications

    • 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
    • B01D53/228—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 characterised by specific 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
    • B01D71/06—Organic material
    • B01D71/38—Polyalkenylalcohols; Polyalkenylesters; Polyalkenylethers; Polyalkenylaldehydes; Polyalkenylketones; Polyalkenylacetals; Polyalkenylketals
    • B01D71/381—Polyvinylalcohol
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
    • B01D71/401—Polymers based on the polymerisation of acrylic acid, e.g. polyacrylate
    • B01D71/4011—Polymethylmethacrylate
    • 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
    • B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
    • B01D71/80—Block polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/42—Details of membrane preparation apparatus
    • 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 complex for acidic gas separation, a method for producing the same, and an acidic gas separation module.
  • Gas separation membranes that selectively separate gases such as carbon dioxide are broadly classified into facilitated transport membranes and dissolved diffusion membranes.
  • separation is performed by utilizing the difference between the solubility of the separation gas and the substance to be separated in the membrane and the diffusivity in the membrane.
  • the degree of separation by the membrane is uniquely determined when the material and physical properties of the membrane are determined.
  • the facilitated transport membrane contains a carrier in the membrane and transports the separation gas to the opposite side of the membrane by this carrier. In this case, since the carrier is contained in the film, the solubility of carbon dioxide and the like is remarkably increased, and transport can be performed satisfactorily.
  • a CO 2 facilitated transport film having a CO 2 / H 2 selective performance by supporting a gel layer containing cesium carbonate or the like in a moisture-containing gel on a hydrophilic porous film. It is disclosed that it can be applied to a CO 2 permeable membrane reactor (see, for example, Japanese Patent No. 4621295).
  • the present invention has been made in view of the above, and a method for producing a complex for acidic gas separation that is stably produced while suppressing the occurrence of blocking of the acidic gas separation layer while maintaining high acid gas separation ability,
  • An object of the present invention is to provide a complex for acidic gas separation and an acidic gas separation module that have high acid gas separation performance and excellent productivity, and to achieve the object.
  • ⁇ 1> (1) a compound selected from the group consisting of an alkyl group having 3 to 20 carbon atoms or a fluorinated alkyl group having 3 to 20 carbon atoms and a hydrophilic group; and (2) a compound having a siloxane structure; (3) At least one selected from polymer particles having an average particle diameter of 0.01 ⁇ m to 1000 ⁇ m and a specific gravity of 0.5 g / cm 3 to 1.3 g / cm 3 , a water absorbing polymer, and an alkali metal salt.
  • a coating solution preparing step of preparing a coating solution for forming an acidic gas separation layer containing a carbon dioxide carrier a coating step of coating the coating solution for forming an acidic gas separation layer on a long porous support
  • To acid gas Delamination is a manufacturing method for acid gas separation composite to produce acid gases separation complex with.
  • ⁇ 2> The total content of the compound having a C 3-20 alkyl group or a C 3-20 fluorinated alkyl group and a hydrophilic group, and the compound having a siloxane structure in the acidic gas separation layer.
  • the content of the compound having a C 3-20 alkyl group or a C 3-20 fluorinated alkyl group and a hydrophilic group in the acidic gas separation layer is such that the total content of the acidic gas separation layer
  • the content of the compound having a siloxane structure in the acidic gas separation layer is 0.01% by mass to 10% by mass with respect to the total solid content of the acidic gas separation layer. It is a manufacturing method of the complex for acidic gas separation as described in any one of ⁇ 3>.
  • ⁇ 5> The composite for acidic gas separation according to any one of ⁇ 1> to ⁇ 4>, wherein the area occupied by the polymer particles on the surface of the acidic gas separation layer is 0.1% to 60% It is a manufacturing method of a body.
  • ⁇ 6> The compound having an alkyl group having 3 to 20 carbon atoms or a fluorinated alkyl group having 3 to 20 carbon atoms and a hydrophilic group has a molecular weight of 60 to 2,000. It is a manufacturing method of the complex for acidic gas separation as described in any one.
  • At least one selected from polymer particles having a specific gravity of 0.5 g / cm 3 to 1.3 g / cm 3 having a specific gravity of 0.5 to 1.3 g / cm 3 is a compound having an alkyl group having 3 to 20 carbon atoms and a hydrophilic group ⁇ 1> to ⁇ 3> and the method for producing a complex for acidic gas separation according to any one of ⁇ 6>.
  • At least one selected from polymer particles having a specific gravity of 0.5 g / cm 3 to 1.3 g / cm 3 having a specific gravity of 0.5 to 1.3 g / cm 3 is a compound having a fluorinated alkyl group having 3 to 20 carbon atoms and a hydrophilic group.
  • the method for producing a complex for acidic gas separation according to any one of the above.
  • a polymer particle of 1.3 g / cm 3 ⁇ 1> or the item ⁇ 5> is a method for producing the acid gas separation composite according to.
  • ⁇ 12> comprising two kinds of the alkali metal salts, wherein one of the two kinds is selected from the group consisting of a rubidium salt and a cesium salt, and the other alkali metal salt is selected from a potassium salt.
  • complex for acidic gas separation which suppresses generation
  • a complex for acidic gas separation and an acidic gas separation module having high acid gas separation ability and excellent productivity.
  • the present invention is suitable for continuous film formation on a long porous support to roll it, and in this case, the effect of inhibiting blocking of the acidic gas separation layer is further exhibited.
  • FIG. 1 It is a block diagram which shows the example of the manufacturing apparatus of the complex for acidic gas separation which concerns on embodiment of this invention. It is a schematic block diagram which shows an example of the acidic gas separation module which concerns on embodiment of this invention. It is a perspective view showing the cross section of the acidic gas separation module of FIG.
  • the method for producing a complex for acidic gas separation of the present invention comprises (1) a compound having an alkyl group having 3 to 20 carbon atoms or a fluorinated alkyl group having 3 to 20 carbon atoms and a hydrophilic group, and (2) a siloxane structure And (3) at least one selected from polymer particles having an average particle diameter of 0.01 ⁇ m to 1000 ⁇ m and a specific gravity of 0.5 g / cm 3 to 1.3 g / cm 3 ;
  • a film containing a carrier such as an alkali metal salt such as cesium carbonate and transmitting carbon dioxide by this carrier is known.
  • a carrier such as an alkali metal salt such as cesium carbonate and transmitting carbon dioxide by this carrier
  • such membranes often have high deliquescence, and condensation tends to occur on the membrane surface.
  • a continuous film is formed by the roll-to-roll process, blocking occurs, and the film peels off.
  • a surfactant or a polymer component generally used as a lubricant a certain degree of blocking deterrent effect can be expected, but simply including a surfactant or polymer, The material permeability of the membrane is deteriorated, and the gas separation function inherent to the membrane is impaired.
  • the acidic gas separation layer contains specific compounds or polymer particles, and these compounds and particles are unevenly distributed on the surface of the membrane, so that the carbon dioxide gas separation function is maintained well and blocking is suppressed. An effect is given. Since peeling of the film is prevented by blocking inhibition, the production stability in the case of continuous film formation is improved, and as a result, the productivity can be dramatically improved.
  • the “acid gas” in the present invention includes a gas containing carbon dioxide, hydrogen sulfide and the like.
  • a coating liquid for forming an acidic gas separation layer is prepared.
  • the coating solution for forming an acidic gas separation layer in the present invention comprises (A) a compound having an alkyl group having 3 to 20 carbon atoms or a fluorinated alkyl group having 3 to 20 carbon atoms and a hydrophilic group that is a hydrophilic portion as a hydrophobic portion.
  • a compound selected from the group consisting of compounds having a siloxane structure (hereinafter also referred to as “specific compound”) and / or an average particle size of 0.01 ⁇ m to 1000 ⁇ m and a specific gravity of 0.5 g / cm 3 to It comprises 1.3 g / cm 3 polymer particles, (B) a water-absorbing polymer, and (C) a carbon dioxide carrier selected from alkali metal salts.
  • the acidic gas separation layer forming coating solution preferably has a composition containing water, and may further contain other components such as (D) an additive such as a gelling agent, if necessary.
  • Preparation of the coating solution for forming an acidic gas separation layer in the present invention is carried out by adding a specific compound and / or polymer particles, a water-absorbing polymer, a carbon dioxide carrier, and, if necessary, an additive such as a gelling agent in an appropriate amount.
  • a specific compound and / or polymer particles, a water-absorbing polymer, a carbon dioxide carrier, and, if necessary, an additive such as a gelling agent in an appropriate amount. This can be achieved by adding to (normal temperature water or warm water) and thoroughly stirring (heating with stirring if necessary) to promote dissolution.
  • the specific compound and / or polymer particles, the water-absorbing polymer, the carbon dioxide carrier, and, if necessary, the gelling agent may be separately added to water, or may be added in advance. .
  • a specific compound and / or polymer particles, a water-absorbing polymer, and a carbon dioxide carrier are gradually added and stirred to precipitate a water-absorbing polymer (salt). Analysis) can be prevented.
  • the coating solution for forming an acidic gas separation layer according to the present invention comprises (1) an alkyl group having 3 to 20 carbon atoms or a fluorinated alkyl group having 3 to 20 carbon atoms and a hydrophilic portion as a hydrophobic portion.
  • a compound having a certain hydrophilic group (2) a compound having a siloxane structure, and (3) a polymer particle having an average particle diameter of 0.01 ⁇ m to 1000 ⁇ m and a specific gravity of 0.5 g / cm 3 to 1.3 g / cm 3 1 type or 2 types or more selected from the group which consists of three.
  • the specific compound and / or polymer particles are not simply present in the acidic gas separation layer. Is unevenly distributed in the vicinity of the film surface as if the film is formed at first glance. At this time, it is unevenly distributed so that carbon dioxide can permeate. By doing in this way, generation
  • the acidic gas separation layer-forming coating solution contains or does not contain the polymer particles described later, and a compound having an alkyl group having 3 to 20 carbon atoms or a fluorinated alkyl group having 3 to 20 carbon atoms and a hydrophilic group, And one or more compounds selected from the group consisting of compounds having a siloxane structure (specific compounds).
  • the content of the specific compound in the coating solution is preferably from 0.0001 to 1% by mass, more preferably from 0.0003 to 0.8% by mass, and more preferably from 0.001 to 0.8%, based on the total mass of the coating solution. 1% by mass is more preferable.
  • the content of the specific compound is 0.0001% by mass or more, the effect of inhibiting the occurrence of blocking is excellent.
  • the content of the specific compound is 1% by mass or less, the separability of acidic gas such as carbon dioxide is kept good.
  • the compound having an alkyl group having 3 to 20 carbon atoms or a fluorinated alkyl group having 3 to 20 carbon atoms and a hydrophilic group tends to be unevenly distributed so as to cover the surface of the film when a coating film is formed by coating, It is effective in preventing the occurrence of blocking.
  • a surfactant having an alkyl group or a fluorinated alkyl group is hydrophobic in the step of preparing an acid gas separation layer forming coating solution containing the alkyl group and fluorinated alkyl group to form the acid gas separation layer by coating and drying.
  • the compound is oriented on the film surface due to the highly functional alkyl group or fluoroalkyl group, and blocking is effectively prevented by reducing the surface energy of the film surface. Therefore, it is preferable that the compound has a higher hydrophobicity, that is, an alkyl group or fluoroalkyl group having a long carbon chain.
  • a compound having a hydrophobic part and a hydrophilic part which contains an alkyl group having 3 to 20 carbon atoms or a fluorinated alkyl group having 3 to 20 carbon atoms, can be used.
  • Specific examples include surfactants having an alkyl group having 3 to 20 carbon atoms or a fluorinated alkyl group having 3 to 20 carbon atoms in the hydrophobic portion.
  • alkyl group having 3 to 20 carbon atoms examples include groups such as propyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl, and eicosyl. Of these, a long-chain alkyl group is preferable because it is easily distributed on the film surface. Specifically, an alkyl group having 5 to 20 carbon atoms is more preferable, and more preferably 6 to 20 carbon atoms. It is an alkyl group. Among them, the case of having hexyl, octyl, decyl, dodecyl, and eicosyl is particularly preferable as the alkyl group.
  • Examples of the fluorinated alkyl group having 3 to 20 carbon atoms include groups such as fluoropropyl, perfluorobutyl, perfluorohexyl, perfluorooctyl, and perfluorodecyl. Among them, it is preferable to have a fluoroalkyl group having a long carbon chain from the viewpoint of being easily distributed on the film surface, and specifically, a fluorinated alkyl group having 4 to 20 carbon atoms is preferable, more preferably carbon. A fluorinated alkyl group having 5 to 20 carbon atoms, more preferably a fluorinated alkyl group having 6 to 20 carbon atoms. Among them, it is preferable that the fluoroalkyl group has perfluorohexyl, perfluorooctyl, or perfluorodecyl.
  • an alkyl group having no fluorine atom is preferred to a fluorinated alkyl group from the viewpoint of achieving a high level of compatibility between blocking inhibition and excellent acid gas separation.
  • hydrophilic groups include hydroxyl groups, carboxylic acid groups, sulfonic acid groups, phosphoric acid groups, alkyleneoxy groups, amino groups, and quaternary amino groups.
  • Examples of the surfactant having an alkyl group having 3 to 20 carbon atoms or a fluorinated alkyl group having 3 to 20 carbon atoms include the following compounds.
  • Cationic surfactant- Quaternary ammonium salt type
  • Chloride dodecyl dimethyl benzyl ammonium C 12 H 25 N + ( CH 3) 2 CH 2 C 6 H 5 Cl) ⁇ Octyltrimethylammonium chloride (C 8 H 17 N + (CH 3 ) 3 Cl) Decyltrimethylammonium chloride (C 10 H 21 N + (CH 3 ) 3 Cl) ⁇ Dodecyltrimethylammonium chloride (C 12 H 25 N + (CH 3 ) 3 Cl) ⁇ Tetradecyltrimethylammonium chloride (C 14 H 29 N + (CH 3 ) 3 Cl) Cetyltrimethylammonium chloride (CTAC) (C 16 H 33 N + (CH 3 ) 3 Cl) ⁇ Stearyltrimethylammonium chloride (C 18 H 37 N + (CH 3 ) 3 Cl) - hexadecyltrimethylammonium bromide (CTAB) (C 16 H 33 N +
  • Nonionic surfactant (Ester type) Lauric glyceryl (C 11 H 23 COOCH 2 CH (OH) CH 2 OH, w: Glyceryl laurate) ⁇ Glycerol monostearate (C 17 H 35 COOCH 2 CH (OH) CH 2 OH) ⁇ Sorbitan fatty acid ester (RCOOCH 2 CH (CHOH) 3 CH 2 O [R: alkyl having 3 to 20 carbon atoms]) ⁇ Sucrose fatty acid ester (RCOOC 12 H 21 O 10 [R: alkyl having 3 to 20 carbon atoms]) (Ether type) ⁇ Polyoxyethylene alkyl ether (RO (CH 2 CH 2 O) n H [R: alkyl having 3 to 20 carbon atoms]) ⁇ Pentaethylene glycol monododecyl ether (C 12 H 25 O (CH 2 CH 2 O) 5 H, w: Pentaethylene glycol monododecyl ether) -Oct
  • Amphoteric surfactant (Alkyl betaine type) Lauryl betaine (C 12 H 25 N + ( CH 3) 2 CH 2 COO -) Stearyl betaine (C 18 H 37 N + ( CH 3) 2 CH 2 COO -) Dodecyl amino methyl dimethyl sulfopropyl betaine (C 12 H 25 N + ( CH 3) 2 (CH 2) 3 SO 3 -) - octadecyl amino methyl dimethyl sulfopropyl betaine (C 18 H 37 N + ( CH 3) 2 (CH 2) 3 SO 3 -) (Fatty acid amide propyl betaine type) - cocamidopropyl betaine (C 11 H 23 CONH (CH 2) 3 N + (CH 3) 2 CH 2 COO -, w: Cocamidopropyl betaine) ⁇ Cocamidopropyl hydroxysultain (C 11 H 23 CONH (CH 2 ) 3 N + (CH 3 ) 2 CH 2 CHOH
  • the molecular weight of the surfactant having an alkyl group having 3 to 20 carbon atoms or a fluorinated alkyl group having 3 to 20 carbon atoms is preferably in the range of 60 to 2000, and more preferably in the range of 80 to 1500.
  • the molecular weight is 60 or more, it is advantageous in that blocking can be suppressed uniformly as a film surface.
  • the molecular weight is 2000 or less, it is possible to ensure acid gas separation while suppressing blocking.
  • the acidic gas separation layer forming coating solution contains “a surfactant having an alkyl group having 3 to 20 carbon atoms or a fluorinated alkyl group having 3 to 20 carbon atoms”, and an acidic gas separation layer containing the surfactant is provided.
  • the content of the surfactant is preferably 0.01% by mass to 10% by mass, and more preferably 0.01% by mass to 3% by mass with respect to the total solid content of the acidic gas separation layer. It is preferable that When the content of the “surfactant having an alkyl group having 3 to 20 carbon atoms or a fluorinated alkyl group having 3 to 20 carbon atoms” is 0.01% by mass or more, the effect of inhibiting the occurrence of blocking is excellent. Further, when the content of the surfactant is 10% by mass or less, the separability of acidic gas such as carbon dioxide is kept good.
  • a compound having a siloxane structure is likely to be unevenly distributed so as to cover the surface of the film when a coating film is formed by coating, and is effective in inhibiting the occurrence of blocking.
  • the siloxane structure is not particularly limited as long as it has a siloxane skeleton represented by “—Si—O—Si—” as a partial structure.
  • a compound containing a structural unit having a siloxane structure in the side chain is preferable from the viewpoint of enhancing surface segregation when a coating film is formed by application of a coating solution.
  • Siloxane compounds useful for introducing a siloxane structure into the molecule can be obtained from commercially available products such as X-22-173DX and X-22-173BX manufactured by Shin-Etsu Chemical Co., Ltd.
  • One terminal reactive silicone is mentioned.
  • Such a compound can be synthesized by reacting a siloxane having a reactive end with a compound having a cationic polymerizable group.
  • a compound having a hydroxyl group at one end such as Chisso's Silaplane series FM-0411, FM-0421, FM-0425, etc., and epichlorohydrin, or in JP-A-11-80315. It can be synthesized by the method described.
  • Examples of the skeleton structure forming a siloxane structure include the following structures. However, the present invention is not limited to these.
  • the molecular weight of the compound having a siloxane structure is preferably in the range of 200 to 200,000, more preferably in the range of 200 to 150,000, as a weight average molecular weight measured by GPC method.
  • the molecular weight is 200 or more, it is advantageous in that blocking can be uniformly suppressed as a film surface.
  • the molecular weight is 200,000 or less, acid gas separability can be secured while blocking is suppressed.
  • the weight average molecular weight is measured using gel permeation chromatography (GPC) under the following conditions. ⁇ Condition> ⁇ GPC: Alliance (Made by Waters) -Mobile phase solvent: Toluene-Standard sample: Standard polystyrene-Flow rate: 1.0 ml / min -Column temperature: 40 ° C
  • the acidic gas separation layer forming coating solution contains a compound having a siloxane structure and forms an acidic gas separation layer containing a compound having a siloxane structure
  • the content of the compound having a siloxane structure is It is preferably 0.01% by mass to 10% by mass and more preferably 0.01% by mass to 3% by mass with respect to the total solid content.
  • the content of the compound having a siloxane structure is 0.01% by mass or more, the effect of inhibiting the occurrence of blocking is excellent.
  • the content of the specific compound is 10% by mass or less, the separability of an acidic gas such as carbon dioxide is kept good.
  • Polymer particles for example, particles of polyolefin (eg, polyethylene, polypropylene, polymethylpentene, etc.), polymethyl methacrylate, polystyrene, thermoplastic elastomer, silicone, etc. are preferably mentioned. Among these, polyolefin particles are preferable in that blocking can be uniformly suppressed.
  • polyolefin eg, polyethylene, polypropylene, polymethylpentene, etc.
  • polymethyl methacrylate e.g., polystyrene, thermoplastic elastomer, silicone, etc.
  • polyolefin particles are preferable in that blocking can be uniformly suppressed.
  • the average particle size of the polymer particles is in the range of 0.01 ⁇ m to 1000 ⁇ m.
  • the particle diameter of the polymer particles is less than 0.01 ⁇ m, the particles are too densely packed, and thus the area occupied on the film surface when the coating film is formed cannot be ensured without reducing the separation performance.
  • the average particle diameter of the polymer particles exceeds 1000 ⁇ m, too much polymer is present on the film surface when the coating film is formed, and the carbon dioxide permeability is lowered and the polymer particles may fall off.
  • the average particle diameter of the polymer particles is more preferably in the range of 0.02 ⁇ m to 750 ⁇ m, still more preferably in the range of 0.03 ⁇ m to 500 ⁇ m, and particularly preferably in the range of 0.1 ⁇ m to 50 ⁇ m.
  • the particle diameter of the polymer particles is a value measured using FPAR1000 manufactured by Otsuka Electronics Co., Ltd.
  • the specific gravity of the polymer particles is in the range of 0.5 g / cm 3 to 1.3 g / cm 3 . If the specific gravity of the polymer particles is less than 0.5 g / cm 3 and is too small, the membrane surface tends to be clogged, and rather the carbon dioxide permeability is impaired. In addition, when the specific gravity of the polymer particles exceeds 1.3 g / cm 3 , it becomes easy to settle in the coating solution, and it becomes difficult for the polymer to exist on the film surface when the coating film is formed, so that the blocking inhibition effect is lowered. . Among these, as the specific gravity of the polymer particles, more preferably in the range of 0.52g / cm 3 ⁇ 1.28g / cm 3, more preferably in the range of from 0.55g / cm 3 ⁇ 1.27g / cm 3.
  • the polymer particles can be used, for example, in the form of an emulsion (emulsion) in which a polymer is dispersed in a liquid state in an aqueous medium and a dispersion (suspension) in which a polymer is dispersed in a solid state in an aqueous medium. .
  • polystyrene resin particles As the polymer particles, commercially available products may be used. For example, Chemipearl w-308, w-400, w-100, wp-100, and A-100 manufactured by Mitsui Chemicals, Inc. may be used. Can be used.
  • the total content of the polymer particles in the coating liquid is such that the area occupied by the polymer particles on the surface of the acidic gas separation layer is 0.1% to 60%.
  • An amount is preferred.
  • the occupied area by the polymer particles is 0.1% or more, the effect of inhibiting the occurrence of blocking is excellent. Further, when the area occupied by the polymer particles is 60% or less, the acid gas separability can be kept good while blocking is suppressed.
  • the occupied area of the polymer particles is more preferably 0.5% to 30%, further preferably 1% to 10%.
  • the occupied area is determined by image analysis of the particle coverage per unit area using a scanning electron microscope (JSM6610, manufactured by JEOL).
  • the polymer particles When an acidic gas separation layer is formed by coating with polymer particles, the polymer particles have a low specific gravity. Therefore, in the process of forming a coating film using a coating liquid containing polymer particles and drying, the polymer particles are formed on the coating film surface. It is unevenly distributed. Thereby, the polymer particles are unevenly distributed on the surface to prevent blocking without performing a special treatment such as applying only to the surface.
  • the acidic gas separation layer is prepared by preparing a first coating solution containing polymer particles and the specific compound, and a second coating solution containing no polymer particles and the specific compound, respectively, on the porous support.
  • the polymer particles and the specific compound can be formed as a layer unevenly distributed on the film surface. Since these compounds and polymer particles are not compatible with other components constituting the separation layer, they do not impair the separation ability inherent in the separation layer.
  • the coating solution for forming an acidic gas separation layer in the invention contains at least one water-absorbing polymer.
  • the water-absorbing polymer functions as a binder, and retains moisture and exerts a function of separating a gas such as carbon dioxide by a carrier.
  • the water-absorbing polymer is preferably one having high water absorption from the viewpoint of being able to dissolve in water to form a coating solution and imparting high water absorption (moisturizing property) to the acidic gas separation layer.
  • the physiological saline preferably has a water absorption of 0.5 g / g or more, more preferably 1 g / g or more, and more preferably 5 g / g or more.
  • the water absorption is preferably 10 g / g or more, more preferably 20 g / g or more, and most preferably 20 g / g or more.
  • water-absorbing polymer conventionally known hydrophilic polymers can be used. From the viewpoint of water absorption, film-forming property, strength, etc., for example, polyvinyl alcohols, polyacrylic acids, polyethylene oxides, water-soluble celluloses. , Starches, alginic acids, chitins, polysulfonic acids, polyhydroxymethacrylates, polyvinylpyrrolidones, polyNvinylacetamides, polyacrylamides, polyethyleneimines, polyallylamines, polyvinylamines and the like are preferred. Moreover, these copolymers are also suitable as a water absorbing polymer.
  • polyvinyl alcohol and polyvinyl alcohol-polyacrylic acid copolymer are particularly preferable.
  • Polyvinyl alcohol-polyacrylic acid copolymer has a high water absorption capacity and a high strength of hydrogel even at high water absorption.
  • the content of polyacrylate in the polyvinyl alcohol-polyacrylic acid copolymer is, for example, 1 mol% to 95 mol%, preferably 2 mol% to 70 mol%, more preferably 3 mol% to 60 mol%, particularly Preferably, it is 5 mol% to 50 mol%.
  • the polyacrylic acid may form a salt. Examples of the polyacrylate include ammonium salts and organic ammonium salts in addition to alkali metal salts such as sodium salts and potassium salts.
  • polyvinyl alcohol-polyacrylate copolymer sodium salt
  • a commercially available product may be used.
  • the commercially available product include Clastomer AP20 (trade name, manufactured by Kuraray Co., Ltd.).
  • polyvinyl alcohol include PVA117 (trade name, manufactured by Kuraray Co., Ltd.).
  • a water absorbing polymer may be used individually by 1 type, and may mix and use 2 or more types.
  • the content of the water-absorbing polymer in the coating liquid depends on the type, but from the viewpoint of forming a film as a binder and allowing the acid gas separation layer to retain sufficient moisture,
  • the content is preferably 0.5% by mass to 60% by mass, more preferably 0.75% by mass to 55% by mass, and still more preferably 1% by mass to 50% by mass.
  • the coating solution for forming an acidic gas separation layer in the present invention contains one or more alkali metal salts as a carbon dioxide carrier.
  • the carbon dioxide carrier functions as a carbon dioxide carrier in the membrane in the separation of carbon dioxide.
  • the number of types of alkali metal salts is determined by the type of alkali metal, and even if the counter ions are different, they are not counted as different types. That is, even if potassium carbonate and potassium hydroxide are used in combination, it is counted as one type.
  • the alkali metal salt is preferably one having an affinity for carbon dioxide and exhibiting water solubility, and a known one can be used.
  • the carrier is a substance having an affinity for carbon dioxide, and various water-soluble inorganic and organic substances showing basicity are used.
  • a complex compound added with a polydentate ligand that forms a complex with each other ammonia, ammonium salts, various linear and cyclic amines, amine salts, ammonium salts, and the like.
  • These water-soluble derivatives can also be preferably used.
  • amine-containing compounds that are difficult to evaporate such as amino acids and betaines, can be used.
  • an alkali metal carbonate is preferable.
  • the alkali metal salt is preferably a salt selected from the group consisting of a rubidium salt, a cesium salt, and a potassium salt in terms of high solubility in water, and among them, a rubidium carbonate and a cesium carbonate are more preferable.
  • 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, cesium hydroxide, and rubidium hydroxide.
  • the content of the alkali metal salt in the coating solution depends on the type of the coating solution. However, in order to prevent salting out before coating and to ensure that the separation gas is separated, the content of the alkali metal salt is 0 0.1 mass% to 30 mass% is preferable, 0.2 mass% to 25 mass% is more preferable, and 0.3 mass% to 20 mass% is particularly preferable.
  • one of the two alkali metal salts is preferably selected from the group consisting of a rubidium salt and a cesium salt, and the other is preferably selected from a potassium salt.
  • the content of the alkali metal salt is shown in relation to the total mass of the solid content including the water-absorbing polymer as the main component of the film and two or more alkali metal salts, the total of the two or more alkali metal salts
  • the mass ratio is preferably 25% by mass or more and 85% by mass or less, and more preferably 30% by mass or more and 80% by mass or less. By setting this amount within the above range, the acid gas separation function can be sufficiently exhibited.
  • one of the two types of alkali metal salts is the total mass of solids containing the water-absorbing polymer and two or more types of alkali metal salts (typically the total mass of the acid gas separation layer after drying) ) To 0.01% by mass or more, and more preferably 0.02% by mass or more. Although there is no upper limit in particular, it is preferable that it is 10 mass% or less, and it is more preferable that it is 7.5 mass% or less. When the amount is in the above range, it is advantageous for preventing blocking, and when the amount is not too much, it is advantageous for maintaining good handling.
  • two or more alkali metal salts are preferably used from the viewpoint of inhibiting the occurrence of blocking, and a combination of two alkali metal salts is preferred.
  • combinations of alkali metal salts the following # 1 to # 3 are preferable.
  • an alkali metal salt is indicated by the name of an alkali metal, but this means that the salt or ion of the metal may be used.
  • the ratio of both in the case of containing two kinds of alkali metal salts is not particularly limited, but it is preferable that the other is 50 parts by mass or more with respect to 100 parts by mass of one of the two kinds of alkali metal salts. More preferably, it is at least part by mass. As an upper limit, 100,000 mass parts or less are preferable, and 80,000 mass parts or less are more preferable.
  • the coating liquid for acidic gas separation layer formation in this invention may be comprised using other components, such as a crosslinking agent and surfactant.
  • Crosslinking of the water-absorbing polymer can be carried out by a conventionally known method such as thermal crosslinking, ultraviolet crosslinking, electron beam crosslinking, or radiation crosslinking. It is preferable that the coating solution for forming an acidic gas separation layer (or a single dioxide separation layer) in the present invention contains a crosslinking agent. In particular, it contains a polyvinyl alcohol-polyacrylate copolymer as a water-absorbing polymer, and a crosslinking agent having two or more functional groups that can be thermally crosslinked by reacting with the polyvinyl alcohol-polyacrylate copolymer. Are preferred.
  • crosslinking agent examples include polyvalent glycidyl ether, polyhydric alcohol, polyvalent isocyanate, polyvalent aziridine, haloepoxy compound, polyvalent aldehyde (for example, glutaraldehyde), polyvalent amine and the like.
  • the coating solution for forming an acidic gas separation layer (or a single dioxide separation layer) in the present invention is a specific compound and / or polymer particles, a water-absorbing polymer as long as it does not adversely affect the film forming property (coating property) and the acidic gas separation property.
  • other components such as additives in addition to alkali metal salts and the like. Examples of other components include, in addition to a crosslinking agent, for example, surfactants other than those described above, catalysts, moisturizing (water absorbing) agents, auxiliary solvents, film strength adjusting agents, and defect detecting agents.
  • FIG. 1 shows the overall configuration of a production apparatus for producing an acid gas separation composite.
  • the acidic gas separation complex manufacturing apparatus 110 includes a delivery roller 114 that is an example of a conveying unit that feeds a long porous support 112 in a fixed direction, and a porous support 112.
  • a drying unit 120 which is an example of a drying apparatus that is dried in contact state to form an acidic gas separation layer, and is disposed downstream of the drying unit 120 in the support conveyance direction, and is separated on the support 112.
  • the delivery roller 114 is provided with an axis 114A around which the support 112 is wound, and the support 112 is delivered by rotating the shaft 114A in the direction of the arrow. Then, with the back surface side of the support body 112 wound around a plurality of back surface support rollers 124, the support body 112 is conveyed in a certain direction and sequentially sent to the coating device 116, the cooling unit 118, and the drying unit 120. ing.
  • the acidic gas separating composite 140 manufactured via these is wound around the winding roller 122.
  • the take-up roller 122 is provided with a shaft core 122A for winding the acid gas separating composite 140, and the acid gas separating composite 140 is rotated by rotating the shaft 122A in the direction of the arrow by a motor (not shown). Is wound around the shaft core 122A at a predetermined speed.
  • the acidic gas separation layer forming coating solution as described above is used, and this is applied to the porous support by the roll-to-roll processing as shown in FIG. Blocking at the time of producing the composite for acidic gas separation by continuously forming the separation layer is effectively prevented. Therefore, the yield due to film peeling that is likely to occur particularly in the manufacturing process by the roll-to-roll method can be suppressed. Therefore, the production method of the present invention is highly suitable for producing a complex for acid gas separation.
  • the acidic gas separation layer forming coating solution prepared in the coating solution preparing step is applied onto the long porous support.
  • the long porous support 112 is sent out from the feed roller 114, transported to a coating position by the coating die 136 of the coating device 116, and placed on the porous support 112.
  • a coating film is formed by applying the coating liquid.
  • the coating device 116 includes a storage part 116A in which the acidic gas separation layer forming coating liquid is stored, and a coating die 136 through which the coating liquid stored in the storage part 116A flows.
  • the coating die 136 can freely adjust the flow rate of the coating solution and the gap width between the porous support 112 and can be applied to various thicknesses of the support.
  • the reservoir 116A is provided with a heater (not shown) for adjusting the temperature of the coating liquid and a stirring device for stirring the coating liquid.
  • the temperature of the coating solution in the coating process decreases, the viscosity may increase, or the water-absorbing polymer may precipitate (salt out), making it difficult to apply to the porous support, and the film thickness variation may increase. . Therefore, it is preferable to keep the temperature so that gelation or salting-out does not occur after the coating solution is prepared and before it is applied.
  • the temperature of the coating solution in the coating process may be set so that gelation or salting-out does not occur depending on the composition and concentration, but if the temperature is too high, the composition concentration changes due to the evaporation of water from the coating solution.
  • the gelation may proceed locally, so that the temperature is usually 50 ° C. or higher, preferably about 60 to 85 ° C.
  • the coating device 116 is not limited to the above configuration, and examples thereof include a curtain flow coater, an extrusion die coater, an air doctor coater, a blade coater, a rod coater, a knife coater, a squeeze coater, a reverse roll coater, and a bar coater. Can be mentioned.
  • an extrusion die coater is preferable from the viewpoint of film thickness uniformity, coating amount, and the like.
  • the coating amount of the coating solution depends on the composition and concentration of the coating solution, but if the coating amount per unit area is too small, pores may be formed in the membrane during the drying step (or cooling step), or as an acidic gas separation layer The strength may be insufficient. On the other hand, if the coating amount is too large, the variation in film thickness becomes large, or the thickness of the resulting acidic gas separation layer becomes too large, which may reduce the carbon dioxide permeability. From the above viewpoint, the coating amount is preferably adjusted so that the thickness of the acidic gas separation layer obtained through the drying step is 1 ⁇ m to 100 ⁇ m, more preferably 2 ⁇ m to 90 ⁇ m, and particularly preferably 3 ⁇ m to 80 ⁇ m. .
  • porous support From the viewpoint of continuous film formation by a roll-to-roll method, a long support is used as the porous support (hereinafter also simply referred to as a support).
  • the material for the porous support is not particularly limited, but is preferably a porous material that supports the acidic gas separation layer and has good carbon dioxide permeability.
  • the porous support is preferably one that can form an acidic gas separation layer in a desired form by applying a coating solution.
  • Suitable materials for the porous support include paper, fine paper, coated paper, cast coated paper, synthetic paper, and cellulose, polyester, polyolefin, polyamide, polyimide, polysulfone aramid, polycarbonate, metal, glass, ceramics, etc. It is. More specifically, resin materials such as polypropylene, polyethylene, polystyrene, polyphenyl sulfide, polyether imide, polyether ether ketone, polysulfone, polyether sulfone, polyethylene terephthalate, polytetrafluoroethylene, and polyvinylidene fluoride are preferable. It is mentioned in. Among these, polyolefin and its fluoride are particularly preferable from the viewpoint of stability over time.
  • a woven fabric, a non-woven fabric, a porous membrane or the like can be adopted.
  • a support having a high self-supporting property and a high porosity can be suitably used.
  • Expanded porous membranes of polypropylene, polyethylene, polytetrafluoroethylene, and polyvinylidene fluoride, and phase separation membranes of polysulfone and polyacrylonitrile have high porosity, low diffusion inhibition of separation gases such as carbon dioxide, strength, and suitability for production. From the viewpoint of Among these, a stretched film of polytetrafluoroethylene (PTFE) is particularly preferable.
  • PTFE polytetrafluoroethylene
  • an inorganic material or an organic-inorganic hybrid material may be used.
  • the inorganic support include a porous substrate mainly composed of ceramics. By using ceramics as a main component, it is excellent in heat resistance, corrosion resistance, etc., and mechanical strength can be increased.
  • the type of ceramic is not particularly limited, and any commonly used ceramic can be employed. Examples thereof include alumina, silica, silica-alumina, mullite, cordierite, zirconia and the like. Moreover, you may adjust by compounding 2 or more types of ceramics, or ceramics and a metal, or compounding ceramics and an organic compound.
  • the thickness of the support is preferably 30 ⁇ m to 500 ⁇ m, more preferably 50 ⁇ m to 400 ⁇ m, and particularly preferably 50 ⁇ m to 350 ⁇ m.
  • the strength of the porous support is 10 N so that the support is not distorted or broken in the roll-to-roll method. / 10 mm or more (tensile speed 10 mm / min) is preferable.
  • the coating film formed by coating in the coating step is dried to form an acidic gas separation layer, thereby obtaining a complex for acidic gas separation.
  • the drying unit 120 provided in the support conveyance path the gel film on the support 112 that has been gelled by the cooling unit 118 is dried and thermally cross-linked to produce an acidic gas. A separation layer is obtained.
  • hot air dry air
  • the film after the cooling process described later is immobilized in a gel form, it is dried without collapsing even when directly applied with a drying wind.
  • the wind speed of the drying air can be set so that the coating film (or the gel film when the cooling process is performed) can be dried quickly and the coating film (or the gel film) does not collapse, for example, 1 m / min to 80 m / min. More preferably, it is 2 to 70 m / min, more preferably 3 to 40 m / min. In this embodiment, the wind speed is 30 m / min.
  • the temperature of the drying air is preferably set to 20 ° C. to 80 ° C. from the viewpoint that the porous support is not deformed and the coating film (the gel film when the cooling process is performed) is quickly dried. It is more preferably 25 ° C. to 70 ° C., further preferably 30 ° C. to 60 ° C. In this embodiment, the temperature of the drying air is about 40 ° C.
  • Drying and cross-linking in the drying step may be performed simultaneously or separately.
  • a drying means such as an infrared heater, or may be cross-linked with hot air by drying.
  • Thermal crosslinking can be performed by heating to about 100 to 150 ° C., for example.
  • the drying unit 120 of the present embodiment includes a housing 120A into which the support body 112 is carried in and out, a plurality of hot air heaters 132 arranged in the housing 120A and drying the gel film on the surface of the support body 112, and a plurality of hot air heaters 132 And a halogen heater 134.
  • the hot air heater 132 is disposed at a predetermined interval with respect to the surface of the support 112, and blows hot air on the surface of the support 112 to dry the gel film on the support 112.
  • the halogen heater 134 is disposed at a predetermined interval with respect to the surface of the support 112, and dries the gel film on the support 112 with heat.
  • a plurality of hot air heaters 132 and halogen heaters 134 are alternately arranged.
  • the gel film on the surface of the support 112 is dried and thermally crosslinked by these hot air heaters 132 and halogen heaters 134 to be acidic.
  • a gas separation layer is obtained.
  • a plurality of hot air heaters 132 and halogen heaters 134 are alternately arranged.
  • the present invention is not limited to this configuration. For example, a configuration including only a plurality of hot air heaters 132 may be used.
  • a coating device and a drying device for forming a carrier elution preventing layer may be provided on the separation layer.
  • a cooling process for cooling the coating film formed by coating to obtain a gel film may be provided.
  • a drying step is provided after the cooling step for obtaining the gel film.
  • the gel film obtained from the coating film is dried to form an acid gas separation layer, thereby obtaining a complex for acid gas separation.
  • the coating liquid in the case of providing a cooling step is preferably prepared to have a composition such that the liquid film is gelled within 120 seconds when left at 12 ° C. with a thickness of 1 mm or less, and the liquid does not fall due to gravity.
  • a cooling step the suitability for producing a complex for acidic gas separation can be achieved by sequentially carrying out the coating step, the cooling step, and the drying step while conveying the porous support in a certain direction. Can be further improved.
  • the gel film obtained has a thickness of 30 ⁇ m or more, more preferably 50 ⁇ m or more, and particularly preferably 100 ⁇ m or more.
  • the complex for acidic gas separation of the present invention is provided with a porous support, the porous support, and (1) an alkyl group having 3 to 20 carbon atoms or a fluorinated alkyl group and a hydrophilic group. And (2) a compound selected from the group consisting of compounds having a siloxane structure (specific compound) and (3) an average particle size of 0.01 ⁇ m to 1000 ⁇ m and a specific gravity of 0.5 g / cm 3 to 1.3 g /
  • An acidic gas separation layer including at least one selected from polymer particles of cm 3 , a water-absorbing polymer, and a carbon dioxide carrier selected from an alkali metal salt is provided.
  • the thickness of the acidic gas separation layer constituting the complex for acidic gas separation is preferably 5 ⁇ m to 50 ⁇ m, more preferably 10 ⁇ m to 40 ⁇ m, and particularly preferably 15 ⁇ m to 30 ⁇ m. When the thickness is 50 ⁇ m or less, the acid gas separation property is more excellent. When the thickness is 5 ⁇ m or more, the mechanical strength as the separation membrane can be maintained.
  • porous support constituting the acidic gas separation composite Details of the porous support constituting the acidic gas separation composite, the specific compound constituting the acidic gas separation layer, the water-absorbing polymer, the alkali metal salt (carbon dioxide carrier), etc. are as described above. The preferred embodiments are also the same.
  • the content of the specific compound in the acidic gas separation layer is preferably 0.01% by mass to 10% by mass and more preferably 0.02% by mass to 8% by mass with respect to the total solid content. It is excellent in the blocking inhibitory effect because content of a specific compound is 0.01 mass% or more. Moreover, when content of a specific compound is 10 mass% or less, it is preferable when making blocking suppression and a carbon dioxide permeability improvement compatible. Further, the content of the polymer particles in the acidic gas separation layer is preferably adjusted so that the occupied area of the polymer particles on the surface of the acidic gas separation layer is in the range described above.
  • the content of the water-absorbing polymer in the acidic gas separation layer is preferably 0.5% by mass to 60% by mass, more preferably 0.75% by mass to 55% by mass, and more preferably, based on the total solid content. Is more preferably 1% by mass to 50% by mass.
  • content of the water-absorbing polymer is 0.5% by mass or more, it is suitable for securing the strength as a separation membrane.
  • content of a water absorbing polymer is 60 mass% or less, it is advantageous at the point of separation performance.
  • the content of the alkali metal salt in the acidic gas separation layer is preferably 25% by mass to 85% by mass and more preferably 30% by mass to 80% by mass with respect to the total solid content.
  • the content of the alkali metal salt is 25% by mass or more, carbon dioxide permeability can be favorably maintained. Further, when the content of the alkali metal salt is 85% by mass or less, it is advantageous in that the film strength is maintained.
  • the composite for acidic gas separation of the present invention may be manufactured by any method as long as it is produced in the above-described configuration, but is most preferably manufactured by the method for manufacturing the composite for acidic gas separation of the present invention described above. Is done.
  • the acid gas separation module of the present invention is provided with the acid gas separation complex produced by the method for producing the acid gas separation complex of the present invention described above or the acid gas separation complex of the present invention described above. Configured.
  • the acidic gas separation complex of the present invention in which a porous support and an acidic gas separation layer are laminated may be installed as a flat membrane, a spiral type known as a reverse osmosis membrane module, For example, it can be used after being processed into a pleated mold having the shape described in JP2010-279885A.
  • a reverse osmosis membrane module for example, it can be used after being processed into a pleated mold having the shape described in JP2010-279885A.
  • an acidic gas separation module incorporating the acidic gas separation layer of the present invention as a spiral type will be described as an example.
  • FIG. 2 is a schematic configuration diagram showing one embodiment of the acidic gas separation module 10 according to the present invention, with a partial cutout
  • FIG. 3 is a perspective view showing a cross section thereof.
  • the spiral type acidic gas separation module 10 has, as its basic structure, an acidic gas separation member 14 which is an example of a complex for acidic gas separation and is adjacent to the porous hollow central tube 12. A single layer or a plurality of laminated bodies made of the flow path members 16 are wound. The periphery of the carbon dioxide separation region formed by the acid gas separation member 14 and the flow path member 16 is covered with a coating layer 18 formed of a material capable of blocking a fluid such as a gas passing through the module. Yes.
  • the acidic gas separation member 14 is a complex for acidic gas separation according to the present invention, which is a laminate in which an acidic gas separation layer and a porous support are laminated.
  • the flow path member 16 used in the acid gas separation module 10 promotes turbulent flow (surface update of the membrane surface) of the supplied fluid to increase the membrane permeation rate of carbon dioxide in the supply fluid, and supply It is preferable to have a function of reducing the pressure loss on the side as much as possible.
  • a net-like channel material 16 is preferably used since it has a function as a spacer and preferably generates a turbulent flow in the fluid. Since the flow path of the fluid changes depending on the shape of the net, the shape of the unit cell of the net is selected from shapes such as a rhombus and a parallelogram according to the purpose.
  • the material of the flow path member 16 is not limited in any way, but since the acidic gas separation member 14 of the present invention is used under a temperature condition of 100 ° C. or higher, a heat resistant material is preferable.
  • the materials mentioned as the material for the porous membrane are also preferably used as the material for the flow path material 16.
  • the acidic gas separation module 10 is a laminate of a polymer compound layer and a porous membrane around the perforated hollow central tube 12 for recovering the separated carbon dioxide.
  • a region for separating carbon dioxide formed by winding the (acid gas separation member) 14 and the net-like flow path member 16 is provided, and the periphery thereof is covered with a fluid-impermeable coating layer 18.
  • the gas containing carbon dioxide is supplied from the end portion 20 of the acidic gas separation member, and passes through a region for separating carbon dioxide provided with the acidic gas separation member 14 of the present invention, which is partitioned by the coating layer 18.
  • Carbon dioxide separated through the molecular compound layer 14 is collected in the hollow central tube 12 and collected from the opening 22 connected to the hollow central tube 12.
  • the remaining gas from which carbon dioxide has been separated that has passed through the voids of the porous membrane and the flow path material 16 in the acidic gas separation member 14 is, in the acidic gas separation module 10, an opening 22 for carbon dioxide recovery. Is discharged from the end 24 of the acid gas separation member.
  • a carrier gas selected from an inert gas or the like may be supplied to the hollow central tube 12 for carbon dioxide recovery.
  • Example 1 Clastomer AP-20 (manufactured by Kuraray Co., Ltd .; polyvinyl alcohol-polyacrylate copolymer (absorbing polymer)) 2.4 mass% and 25 mass% glutaraldehyde aqueous solution (manufactured by Wako; cross-linking agent) 0.01 mass 1M hydrochloric acid was added to an aqueous solution containing 1% until the pH reached 1, and crosslinking was performed. Thereafter, an aqueous solution of 40% by mass of cesium carbonate (manufactured by Rare Products Metals; alkali metal salt) was added so that the cesium carbonate concentration was 6.0% by mass.
  • cesium carbonate manufactured by Rare Products Metals; alkali metal salt
  • potassium carbonate (Wako company make; alkali metal salt) aqueous solution was added so that potassium carbonate concentration might be 0.61 mass%.
  • a PTFE / PP nonwoven fabric manufactured by GE
  • a porous support Apply the coating solution obtained on this nonwoven fabric, and dry it to form a separation membrane (1) that functions as an acidic gas separation layer.
  • the content of the surfactant was 0.05% by mass with respect to the total solid content of the separation membrane (1).
  • Example 2 In Example 1, 0.003% by mass of 1% by mass of Lapisol A-90 (manufactured by NOF Corp .; specific compound) was added to 1% by mass of Zonyl 7950 (manufactured by Aldrich; fluorinated alkyl group having 3 or more carbon atoms and an ester group.
  • a separation membrane (2) functioning as an acidic gas separation layer was produced in the same manner as in Example 1 except that the amount of the surfactant (specific compound) was changed to 0.003% by mass.
  • Example 3 In Example 1, 0.003% by mass of 1% by mass of Lapisol A-90 (manufactured by NOF Corp .; specific compound), 1% by mass of Surflon S231 (manufactured by AGC Seimi Chemical Co., Ltd .; fluorinated alkyl group having 3 or more carbon atoms) A separation membrane (3) functioning as an acidic gas separation layer was produced in the same manner as in Example 1 except that the surfactant (specific compound) was changed to 0.003% by mass.
  • Example 5 In Example 1, 0.003% by mass of 1% by mass of Lapisol A-90 (manufactured by NOF Corp .; specific compound) was added to 1% by mass of Chemipearl w-308 (manufactured by Mitsui Chemicals, Inc., average particle size: 7 ⁇ m, specific gravity). : 0.97 g / cm 3 , true spherical polyethylene particles (polymer particles)) Separation membrane (5) functioning as an acidic gas separation layer in the same manner as in Example 1 except that it was changed to 0.003% by mass. Was made. The occupied area (covered area) by the polyethylene particles in the produced separation membrane was 8.2%. The occupied area was determined by image analysis of the particle coverage per unit area using a scanning electron microscope (JSM6610, manufactured by JEOL).
  • Example 6 In Example 1, 0.003% by mass of 1% by mass of Lapisol A-90 (manufactured by NOF Corp .; specific compound) is converted into X-22-170BX (manufactured by Shin-Etsu Chemical Co., Ltd .; compound having a siloxane structure (specific compound)). A separation membrane (6) functioning as an acidic gas separation layer was produced in the same manner as in Example 1 except that the amount was changed to 0.003 mass%.
  • Example 7 In Example 1, the addition amount of 1% by mass of Lapisol A-90 (manufactured by NOF Corporation; specific compound) was changed from 0.003% by mass to 0.1 (Example 7), 0.01 (Example 8). Separation membranes (7) to (8) functioning as an acidic gas separation layer were produced in the same manner as in Example 1 except that the change was made.
  • the surfactant content was 1.4% by mass (Example 7) and 0.14% by mass (Example 8) based on the total solid content of the separation membrane (1).
  • Example 9 In Example 5, 0.003% by mass of 1% by mass of Chemipearl w-308 (polyethylene particles; polymer particles) was changed to 1% by mass of Chemipearl wp-100 (Mitsui Chemicals, average particle size: 1.0 ⁇ m, specific gravity: 0). .9 g / cm 3 , polypropylene particles (polymer particles)) A separation membrane (9) functioning as an acidic gas separation layer was produced in the same manner as in Example 5 except that the amount was changed to 0.003% by mass.
  • Example 2 (Comparative Example 2) In Example 5, 0.003% by mass of 1% by mass Chemipearl w-308 (polyethylene particles; polymer particles) was added to KE-S50 (manufactured by Nippon Shokubai Co., Ltd., average particle size: 0.5 ⁇ m, specific gravity: 2.0 g / cm). 3 and silica particles) A separation membrane (11) functioning as an acidic gas separation layer was produced in the same manner as in Example 5 except that the amount was changed to 0.003% by mass.

Landscapes

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

Abstract

La présente invention a une étape pour préparer d'un liquide de revêtement pour former une couche de séparation de gaz acide, une étape pour revêtir un long support poreux par le liquide de revêtement pour former une couche de séparation de gaz acide et une étape pour sécher la couche de revêtement appliquée en revêtement pour créer une couche de séparation de gaz acide. Une couche de séparation de gaz acide est formée de façon continue tandis que le support poreux est transporté dans une direction fixée et un complexe de séparation de gaz acide ayant une couche de séparation de gaz acide sur le support poreux est fabriqué. Le liquide de revêtement contient un polymère absorbant l'eau, un support de dioxyde de carbone choisi parmi les sels de métaux alcalins et au moins une matière choisie parmi des particules polymères ayant une dimension moyenne de 0,01-1 000 µm et une masse volumique de 0,5-1,3 g/cm3 et un composé choisi dans le groupe consistant en les composés ayant un groupe alkyle ou groupe fluoroalkyle en C3-20 et un groupe hydrophile, et des composés ayant une structure siloxane.
PCT/JP2013/068421 2012-07-11 2013-07-04 Complexe de séparation de gaz acide, son procédé de fabrication et module de séparation de gaz acide WO2014010512A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2012155923A JP2014014806A (ja) 2012-07-11 2012-07-11 酸性ガス分離用複合体及びその製造方法並びに酸性ガス分離モジュール
JP2012-155923 2012-07-11

Publications (1)

Publication Number Publication Date
WO2014010512A1 true WO2014010512A1 (fr) 2014-01-16

Family

ID=49915969

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2013/068421 WO2014010512A1 (fr) 2012-07-11 2013-07-04 Complexe de séparation de gaz acide, son procédé de fabrication et module de séparation de gaz acide

Country Status (2)

Country Link
JP (1) JP2014014806A (fr)
WO (1) WO2014010512A1 (fr)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9956541B2 (en) 2014-12-12 2018-05-01 Exxonmobil Research And Engineering Company Methods of separating aromatic compounds from lube base stocks
US10022700B2 (en) 2014-12-12 2018-07-17 Exxonmobil Research And Engineering Company Organosilica materials and uses thereof
US10022701B2 (en) 2014-12-12 2018-07-17 Exxonmobil Research And Engineering Company Coating methods using organosilica materials and uses thereof
US10047304B2 (en) 2014-12-12 2018-08-14 Exxonmobil Research And Engineering Company Aromatic hydrogenation catalysts and uses thereof
US10183272B2 (en) 2014-12-12 2019-01-22 Exxonmobil Research And Engineering Company Adsorbent for heteroatom species removal and uses thereof
US10207249B2 (en) 2014-12-12 2019-02-19 Exxonmobil Research And Engineering Company Organosilica materials and uses thereof
US10435514B2 (en) 2016-06-10 2019-10-08 Exxonmobil Research And Engineering Company Organosilica materials, methods of making, and uses thereof
US10544239B2 (en) 2014-12-12 2020-01-28 Exxonmobile Research And Engineering Company Organosilica materials and uses thereof
US10576453B2 (en) 2014-12-12 2020-03-03 Exxonmobil Research And Engineering Company Membrane fabrication methods using organosilica materials and uses thereof
US10765993B2 (en) 2017-03-31 2020-09-08 Sumitomo Chemical Company, Limited Gel including condensation product of organic silicon compound
US11111352B2 (en) 2017-12-21 2021-09-07 Exxonmobil Research And Engineering Company Methods of producing organosilica materials and uses thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009093666A1 (fr) * 2008-01-24 2009-07-30 Renaissance Energy Research Corporation Membrane à transport facilité du co2 et procédé de fabrication de celle-ci
WO2011099587A1 (fr) * 2010-02-10 2011-08-18 富士フイルム株式会社 Membrane de séparation des gaz, procédé de production associé, et procédé de séparation des gaz, module et appareil de séparation utilisant chacun la membrane de séparation des gaz
WO2011122581A1 (fr) * 2010-03-29 2011-10-06 富士フイルム株式会社 Membrane de séparation de gaz, son procédé de fabrication, procédé de séparation pour un mélange de gaz l'utilisant, module de séparation de gaz et dispositif de séparation de gaz
JP2013027841A (ja) * 2011-07-29 2013-02-07 Fujifilm Corp 二酸化炭素分離部材、その製造方法及び二酸化炭素分離モジュール

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009093666A1 (fr) * 2008-01-24 2009-07-30 Renaissance Energy Research Corporation Membrane à transport facilité du co2 et procédé de fabrication de celle-ci
WO2011099587A1 (fr) * 2010-02-10 2011-08-18 富士フイルム株式会社 Membrane de séparation des gaz, procédé de production associé, et procédé de séparation des gaz, module et appareil de séparation utilisant chacun la membrane de séparation des gaz
WO2011122581A1 (fr) * 2010-03-29 2011-10-06 富士フイルム株式会社 Membrane de séparation de gaz, son procédé de fabrication, procédé de séparation pour un mélange de gaz l'utilisant, module de séparation de gaz et dispositif de séparation de gaz
JP2013027841A (ja) * 2011-07-29 2013-02-07 Fujifilm Corp 二酸化炭素分離部材、その製造方法及び二酸化炭素分離モジュール

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9956541B2 (en) 2014-12-12 2018-05-01 Exxonmobil Research And Engineering Company Methods of separating aromatic compounds from lube base stocks
US10022700B2 (en) 2014-12-12 2018-07-17 Exxonmobil Research And Engineering Company Organosilica materials and uses thereof
US10022701B2 (en) 2014-12-12 2018-07-17 Exxonmobil Research And Engineering Company Coating methods using organosilica materials and uses thereof
US10047304B2 (en) 2014-12-12 2018-08-14 Exxonmobil Research And Engineering Company Aromatic hydrogenation catalysts and uses thereof
US10183272B2 (en) 2014-12-12 2019-01-22 Exxonmobil Research And Engineering Company Adsorbent for heteroatom species removal and uses thereof
US10207249B2 (en) 2014-12-12 2019-02-19 Exxonmobil Research And Engineering Company Organosilica materials and uses thereof
US10544239B2 (en) 2014-12-12 2020-01-28 Exxonmobile Research And Engineering Company Organosilica materials and uses thereof
US10576453B2 (en) 2014-12-12 2020-03-03 Exxonmobil Research And Engineering Company Membrane fabrication methods using organosilica materials and uses thereof
US10661262B2 (en) 2014-12-12 2020-05-26 Exxonmobil Research & Engineering Company Aromatic hydrogenation catalysts and uses thereof
US10435514B2 (en) 2016-06-10 2019-10-08 Exxonmobil Research And Engineering Company Organosilica materials, methods of making, and uses thereof
US10765993B2 (en) 2017-03-31 2020-09-08 Sumitomo Chemical Company, Limited Gel including condensation product of organic silicon compound
US11111352B2 (en) 2017-12-21 2021-09-07 Exxonmobil Research And Engineering Company Methods of producing organosilica materials and uses thereof

Also Published As

Publication number Publication date
JP2014014806A (ja) 2014-01-30

Similar Documents

Publication Publication Date Title
WO2014010512A1 (fr) Complexe de séparation de gaz acide, son procédé de fabrication et module de séparation de gaz acide
TWI614059B (zh) 氣體分離模組與氣體分離系統
US9266066B2 (en) Membrane with localized asymmetries
WO2012096055A1 (fr) Composition pour formation de membrane de séparation de dioxyde de carbone, membrane de séparation de dioxyde de carbone ainsi que procédé de fabrication de celle-ci, et dispositif de séparation de dioxyde de carbone
EP1778388B1 (fr) Separation de gaz par une membrane
KR102066315B1 (ko) 다층 중합체의 혼합 매트릭스 막 제조를 위한 신규 기법 및 막 증류용 장치
TWI716574B (zh) 酸性氣體分離膜及使用該分離膜之酸性氣體分離方法，以及酸性氣體分離模組及酸性氣體分離裝置
EP2365869B1 (fr) Procédé de fabrication d'une membrane microporeuse
US9533262B2 (en) Composite polyamide membrane including dissolvable polymer coating
JP5845513B2 (ja) 孔が大きいポリマー膜
JP5840574B2 (ja) 二酸化炭素分離用複合体の製造方法、二酸化炭素分離用複合体、及び二酸化炭素分離用モジュール
KR101716007B1 (ko) 고성능 폴리아미드계 건식 수처리 분리막 및 그 제조방법
KR102497473B1 (ko) 복합 반투막
Kamio et al. Development of facilitated transport membranes composed of a dense gel layer containing CO2 carrier formed on porous cylindrical support membranes
JP2015027651A (ja) 酸性ガス分離モジュール
JP7127201B2 (ja) 親水性多孔質膜および親水性多孔質膜の製造方法
JP2014039901A (ja) 二酸化炭素分離用複合体の製造方法、二酸化炭素分離用複合体、及びそれを用いた二酸化炭素分離用モジュールの製造方法、並びに二酸化炭素分離用モジュール
JP7177016B2 (ja) 多孔質膜およびフィルターカートリッジ
WO2014050226A1 (fr) Procédé de production d'un complexe de séparation de gaz acide, complexe et module de séparation de gaz acide
JP6013127B2 (ja) ガス分離複合膜、これを用いた分離膜モジュールおよびガス分離システム
JP2014065034A (ja) 酸性ガス分離層、その製造方法及びその促進輸送膜、並びに、酸性ガス分離モジュール及び酸性ガス分離システム
WO2015107820A1 (fr) Module en spirale pour séparer le gaz acide et son procédé de fabrication
JP2014014809A (ja) 二酸化炭素分離用複合体の製造方法、二酸化炭素分離用複合体、二酸化炭素分離モジュール、二酸化炭素分離装置、及び二酸化炭素分離システム
WO2023276483A1 (fr) Membrane d'osmose directe et module de membrane d'osmose directe comprenant celle-ci
KR20220038162A (ko) 기계적으로 안정한 한외 여과 막과 이를 제조하기 위한 방법

Legal Events

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

Ref document number: 13816673

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 13816673

Country of ref document: EP

Kind code of ref document: A1