JP2014079754A - Separation module, manufacturing method of separation module, tube body and winding displacement prevention member - Google Patents

Abstract

PROBLEM TO BE SOLVED: To suppress a pressure loss, and to impart highly efficient separability.SOLUTION: A separation module 10 has: a center pipe 14 having a plurality of through hole groups 14B formed on the outer peripheral surface 14A at intervals in the pipe axial direction A; and a plurality of laminates 16 including a separation membrane 38A for separating a component of a liquid or gas and guiding it to the through hole groups 14B, wound multiply around the center pipe 14 covering each of the plurality of through hole groups 14B, into which a liquid or gas flows from the pipe axial direction A.

Description

  The present invention relates to a separation module, a method for manufacturing the separation module, a tubular body, and a winding deviation prevention member.

  In recent years, development of a separation module that selectively separates gas and water in a raw material has been progressing.

  For example, JP-A-3-249907 discloses a tube having a group of through-holes and a laminate wound around the tube so as to cover the through-holes, and from the water by a separation membrane constituting the laminate. A separation module is disclosed that selectively separates carbon dioxide gas and discharges it from a pipe body through a group of through holes. When the separation module is used, a plurality of separation modules are accommodated in the pressure vessel in order to increase the area of the separation membrane, and the tubes of the separation module are connected to each other by a clamp.

  However, in the separation module disclosed in JP-A-3-249907, when a plurality of separated modules are not correctly connected to each other, a pressure loss occurs at the connection portion, and the separation performance is greatly impaired. Further, when stored in the pressure vessel, when the clamp connection is made in the pressure vessel, the separation module is damaged, and there is a problem that the separation performance is remarkably lowered.

  The present invention has been made in view of the above circumstances, and provides a separation module and a separation module manufacturing method that suppresses pressure loss and has a high-efficiency separation ability, and a tubular body and an anti-winding member related thereto. For the purpose.

The above-described problems of the present invention have been solved by the following means.
The separation module according to the first aspect of the present invention separates a tubular body in which a plurality of through-hole groups are formed on the outer peripheral surface at intervals in the tube axis direction and a liquid or gas component into the through-hole group. A plurality of stacked bodies including a separation membrane for guiding, covering each of the plurality of through-hole groups, being wound around the tube body in a multiple manner, and receiving the liquid or the gas from the tube axis direction. .

  According to this configuration, when the liquid or the gas flows into the stacked body on one end side in the tube axis direction among the multiple stacked bodies, the liquid or the gas is configured by the separation membrane. The elements are separated and guided to the group of through holes. The liquid or gas remaining after separation is sequentially introduced to the stacked body on the other end side in the tube axis direction, and the components are separated. The component separated from each laminated body flows through the through-hole group which each covers from each laminated body, and flows into a pipe body. As described above, since the pipe body is common to the plurality of laminated bodies, it is not necessary to connect the pipe bodies to each other and the pressure loss is suppressed as compared with the case where the laminated bodies have the tubular bodies. Can do. Therefore, the separation module has a highly efficient separation ability.

  In the separation module according to the second aspect of the present invention, in the first aspect, the separation membrane is a facilitated transport type membrane.

  According to this configuration, liquid or gas components are separated by the facilitated transport type membrane.

  In the separation module according to the third aspect of the present invention, in the second aspect, the separation membrane includes a facilitated transport membrane containing a water-soluble polymer compound and a carbon dioxide carrier, and a porous support that supports the facilitated transport membrane. Have.

  According to this configuration, even if water vapor is included in the gas, the water-soluble polymer compound absorbs the water vapor, and the facilitated transport film containing the water-soluble polymer compound retains moisture, thereby Since the carrier can be easily transported, the separation performance is enhanced as compared with the case of using another separation membrane such as a dissolution diffusion membrane.

  In the separation module according to the fourth aspect of the present invention, in the first aspect, the separation membrane is a molecular gate type membrane.

  According to this configuration, liquid or gas components are separated by the molecular gate type film.

  In the separation module according to the fifth aspect of the present invention, in any one of the first to fourth aspects, the winding deviation preventing member that is fitted into both end portions of the laminated body and prevents winding deviation of the laminated body. Have

  According to this structure, the winding shift | offset | difference of all the laminated bodies wound around the pipe body is prevented.

  In the separation module according to a sixth aspect of the present invention, in any one of the first to fifth aspects, the tube body is separated by the inlet into which a sweep gas is introduced and the separation membrane, and the stacked layer is provided. An outlet through which the gas gathered from the through-hole group passes through the body and flows out together with the sweep gas, and a plurality of partition members that are located in the central portion of the through-hole direction in each through-hole group and partition the inside of the pipe. Have.

  According to this configuration, when the sweep gas flows into the pipe body from the inflow port, it hits the plurality of partition members and flows out from the pipe body to the laminate through the through hole group. At this time, the sweep gas sweeps the gas separated by the separation membrane and flows again into the tube body over the partition member. Thereby, the separated gas flows into the tube body through the through hole group without staying in the laminated body, and flows out together with the sweep gas from the outlet. As a result, gas leakage is suppressed and the separation performance is further increased.

  In the separation module according to a seventh aspect of the present invention, in the fifth aspect, the anti-winding prevention member includes a cylindrical portion into which the tubular body is inserted, and an end surface of the laminate that extends radially from the outer peripheral surface of the cylindrical portion. And a cap portion that is provided at a tip portion of the spoke portion, projects to both sides along the tube axis direction, and is fitted into an outer peripheral portion of an end portion of the adjacent laminated body.

  According to this configuration, adjacent laminated bodies can use one winding deviation preventing member in common.

  In the separation module according to an eighth aspect of the present invention, in the seventh aspect, the winding deviation prevention member is divided along the axial direction of the cylindrical portion, and the divided winding deviation prevention members are connected to each other. Connecting means are provided.

  According to this configuration, it is easy to fit the cap portion into the outer peripheral portion of the end portion between adjacent stacked bodies.

  In the separation module according to the ninth aspect of the present invention, in any one of the first to eighth aspects, the tubular body has positioning means for wrapping the laminated body.

  According to this structure, a some laminated body can be wound around a pipe body correctly.

  A method for manufacturing a separation module according to a tenth aspect of the present invention is a manufacturing method for manufacturing the separation module according to any one of the first to ninth aspects, wherein the tube body is rotated about an axis. And a step of winding the plurality of laminated bodies around the tubular body at the same time.

  According to this configuration, the production speed can be increased, and variations in performance between the laminates can be suppressed.

  A tubular body according to an eleventh aspect of the present invention is used in the separation module according to any one of the first aspect to the ninth aspect, and has a plurality of through-hole groups on the outer peripheral surface with an interval in the tube axis direction. .

  According to this structure, a laminated body can be wound for every through-hole group.

  A winding deviation prevention member according to a twelfth aspect of the present invention is a winding deviation prevention member used in the separation module according to the seventh aspect, and includes a cylindrical portion into which the tubular body is inserted, and an outer peripheral surface of the cylindrical portion. A spoke part extending radially from the abutting part and contacting the end face of the laminate, and provided at the tip of the spoke part, projecting to both sides along the tube axis direction, and fitted into the outer peripheral part of the end of the adjacent laminate, respectively. A cap portion.

  According to this configuration, adjacent laminated bodies can use one winding deviation preventing member in common.

  According to the present invention, the pressure loss of the separation module housed in the container is suppressed, and a highly efficient separation ability is achieved.

It is a perspective view which provides the partial notch of the separation module which concerns on embodiment of this invention. It is a perspective view before winding of the laminated body in one separation module unit of the separation module shown in FIG. It is process drawing which shows the manufacturing method of the separation module which concerns on embodiment of this invention. It is process drawing of the manufacturing method of a separation module following FIG. 3A. It is process drawing of the manufacturing method of a separation module following FIG. 3B. It is a perspective view shown in the state where the modification of the telescope prevention board was divided. It is a perspective view shown in the state where the modification of the telescope prevention board was integrated. It is a partial cross section front view shown in the state using the modification of a telescope prevention board. It is a perspective view which shows the modification of a tubular body. It is a perspective view provided with a partial notch of a separation module concerning a reference example of an embodiment of the present invention.

  Hereinafter, a separation module, a method for manufacturing the separation module, a tubular body, and an anti-winding member according to an embodiment of the present invention will be specifically described with reference to the accompanying drawings. In the drawings, members (components) having the same or corresponding functions are denoted by the same reference numerals and description thereof is omitted as appropriate.

<Separation module>
FIG. 1 is a perspective view in which a part of a separation module according to an embodiment of the present invention is provided.

  As shown in FIG. 1, the separation module 10 includes a plurality (three in the present embodiment) of separation module units 12 arranged in a line.

  Each separation module unit 12 has a common central tube 14 that is long in the direction of the row. In each separation module unit 12, the outermost periphery of the laminate 16 is covered with a coating layer 18 in a state where one or more laminates 16 are wound around the central tube 14, and the laminate 16 and the coating layer 18 are covered. Telescope prevention plates 20 are attached to both ends of the lens.

  Each separation module unit 12 having such a configuration is supplied with the raw material gas 22 (or the remaining gas 26) including the carbon dioxide gas 24 and the like from the one end portion 12A side to the laminate 16. When the raw material gas 22 is supplied, each separation module unit 12 separates the raw material gas 22 into the carbon dioxide gas 24 and the remaining gas 26 by the configuration of the laminated body 16 to be described later. The remaining gas 26 is separately discharged from the stacked body 16 on the other end 12B side of each separation module unit 12.

  Since the central tube 14 is common to the units, the central tube 14 is a cylindrical pipe formed longer in the direction of the row than the total length of the separation module units 12. A plurality of through-hole groups 14 </ b> B are formed on the outer peripheral surface 14 </ b> A of the center tube 14 at intervals in the tube axis direction A.

  The number of through-hole groups 14B is the same as the number of separation module units 12 (three in this embodiment). Each through hole group 14 </ b> B is formed in each separation module unit 12, and is not formed between the separation module units 12. The interval between the through-hole groups 14B is longer than the length of the telescope prevention plate 20 in the tube axis direction A in order to facilitate the space of the telescope prevention plate 20 and its attachment.

  The plurality of through-holes 14C constituting the through-hole group 14B penetrate the outer peripheral surface 14A in the radial direction R, and serve as vent holes that ventilate the inside and the outside of the central tube 14.

  An inflow port 30 into which a sweep gas 28 such as an inert gas flows is formed on one end portion side (one end portion 12A side) of the central tube 14. Further, on the other end side (the other end 12B side) of the central tube 14, there is an outlet 32 through which the carbon dioxide gas 24 that permeates the laminated body 16 and collects from the through hole group 14B flows out together with the sweep gas 28. Is formed.

  In addition, a plurality of partition members 34 that are located at the center of the through-hole group 14 </ b> B in the tube axis direction A and partition the inside of the center tube 14 are provided inside the center tube 14.

  The coating layer 18 is formed of a blocking material that can block the source gas 22 that passes through the separation module unit 12.

  The telescope prevention plate 20 is a kind of anti-winding member, and includes a cylindrical portion 20A into which the central tube 14 is inserted, and a spoke portion 20B that extends radially from the outer peripheral surface of the cylindrical portion 20A and contacts the end surface of the laminate 16. And a cap portion 20 </ b> C that is provided at the distal end portion of the spoke portion and is fitted into the outer peripheral portion of the end portion of the laminated body.

  The laminated body 16 covers all of the one through-hole group 14B and is wound around the central tube 14 in a multiple manner. That is, the plurality of stacked bodies 16 cover each of the plurality of through-hole groups 14B one by one. The laminate 16 is sandwiched between carbon dioxide separation layers 38 in which a supply gas passage member 36 is folded in two, and the carbon dioxide separation layer 38 is inserted into the permeate gas passage member 40 inside these radial directions R. It is configured to be bonded through an adhesive portion 42 that has permeated into the substrate. The laminated bodies 16 are bonded to each other through the bonding portion 44 that has penetrated into the carbon dioxide separation layer 38 and stacked around the central tube 14.

  FIG. 2 is a perspective view of the separation module unit 12 of the separation module 10 shown in FIG.

  As shown in FIG. 2, the laminated body 16 is wound around the central tube 14, and then in order from the central tube 14 side, the permeated gas flow path member 40, the carbon dioxide separation layer 38, the supply gas flow path member 36, the carbonic acid The gas separation layer 38 is laminated.

(Supply gas flow path member 36)
The supply gas flow path member 36 is a member to which the source gas 22 including the carbon dioxide gas 24 is supplied from the one end portion 12 </ b> A side of the separation module unit 12, has a function as a spacer, and disturbs the source gas 22. Since it is preferable to generate a flow, a net-like member is preferably used.

  The material of the supply gas flow path member 36 is not limited in any way, but paper, fine paper, coated paper, cast coated paper, synthetic paper, cellulose, polyester, polyolefin, polyamide, polyimide, polysulfone, aramid, Examples thereof include resin materials such as polycarbonate and inorganic materials such as metal, glass and ceramics. The resin materials include polyethylene, polystyrene, polyethylene terephthalate, polytetrafluoroethylene (PTFE), polyethersulfone (PES), polyphenylene sulfide (PPS), polysulfone (PSF), polypropylene (PP), polyimide, polyetherimide, poly Suitable examples include ether ether ketone and polyvinylidene fluoride.

  In addition, preferable materials from the viewpoint of heat and humidity resistance include inorganic materials such as ceramics, glass, and metals, organic resin materials having heat resistance of 100 ° C. or higher, high molecular weight polyester, polyolefin, heat resistant polyamide, polyimide, and the like. Polysulfone, aramid, polycarbonate, metal, glass, ceramics and the like can be suitably used. More specifically, at least one selected from the group consisting of ceramics, polytetrafluoroethylene, polyvinylidene fluoride, polyethersulfone, polyphenylene sulfide, polysulfone, polyimide, polypropylene, polyetherimide, and polyetheretherketone. It is preferable that it is comprised including these materials.

(CO2 separation layer 38)
The carbon dioxide separation layer 38 includes a facilitated transport film 38A provided on the supply gas flow path member 36 side, and a porous support 38B that supports the facilitated transport film 38A and is provided on the permeate gas flow path member 40 side. ,have.

(Promoted transport membrane 38A)
The facilitated transport film 38 </ b> A has a function of selectively transmitting the carbon dioxide gas 24 from the source gas 22. The facilitated transport film 38A preferably contains a carrier that reacts with the carbon dioxide gas 24 in the source gas 22 that passes through the supply gas flow path member 36 and a water-soluble polymer compound that supports the carrier.
In the present embodiment, the facilitated transport film 38A generally has higher heat resistance than the dissolution diffusion film, so that the carbon dioxide gas 24 can be selectively permeated even under a temperature condition of 80 ° C. to 200 ° C., for example. It can be done. Even if the source gas 22 contains water vapor, the water-soluble polymer compound absorbs the water vapor, and the facilitated transport film 38A containing the water-soluble polymer compound retains moisture, so that the carrier further Since it becomes easy to transport, the separation ability is increased as compared with the case where a dissolution diffusion membrane is used.

The facilitated transport film 38A preferably has a cross-linked structure from the viewpoint of heat resistance. From such a viewpoint, a preferred embodiment will be described.
The facilitated transport film 38A is, for example, a water-soluble structure having a crosslinked structure including a hydrolysis-resistant bond selected from the following group (B), which is formed by a single or plural crosslinkable groups selected from the following group (A). It is composed of a conductive polymer compound layer. In particular, from the viewpoint of excellent carbon dioxide separation characteristics and durability, the facilitated transport film 38A is formed of a single crosslinkable group selected from the following group (A), and is selected from the following group (B). It is preferably composed of a water-soluble polymer compound layer having a crosslinked structure containing a hydrolyzable bond.

(A) group: —OH, —NH ₂ , —Cl, —CN, —COOH, epoxy group (B) group: ether bond, acetal bond, —NH—CH ₂ —C (OH) —, —OM —O— (M represents Ti or Zr), —NH—M—O— (M represents Ti or Zr), urethane bond, —CH ₂ —CH (OH) —, amide bond

-Water-soluble polymer compounds-
The water-soluble polymer compound is water-soluble. Here, “water-soluble” means that the polymer compound is soluble in water at 80 ° C. or higher.
The weight average molecular weight of the water-soluble polymer compound is appropriately selected within a range where a stable film can be formed. For example, when having —OH as a crosslinkable group, the weight average molecular weight is 30,000 or more. Is preferred. The weight average molecular weight is more preferably 40,000 or more, and more preferably 50,000 or more. Although there is no restriction | limiting in particular in the upper limit of a weight average molecular weight, From a viewpoint of manufacturing aptitude, it is preferable that it is 6 million or less.
Also, when having -NH ₂ as crosslinkable groups, a weight average molecular weight of those is preferably 10,000 or more. The weight average molecular weight is more preferably 15,000 or more, and more preferably 20,000 or more. Although there is no restriction | limiting in particular in the upper limit of a weight average molecular weight, From a viewpoint of manufacturing aptitude, it is preferable that it is 1 million or less.
The weight average molecular weight of the water-soluble polymer compound is, for example, a value measured according to JIS K 6726 when PVA is used as the water-soluble polymer compound. Moreover, when using a commercial item, the molecular weight nominally used by a catalog, a specification, etc. is used.

As the crosslinkable group of the water-soluble polymer compound, one capable of forming a hydrolysis-resistant crosslinked structure is selected, and a hydroxy group (—OH), an amino group (—NH ₂ ), a carboxy group (—COOH), An epoxy group, a chlorine atom (-Cl), a cyano group (-CN), etc. are mentioned. Among these, an amino group and a hydroxy group are preferable, and a hydroxy group is most preferable from the viewpoint of affinity with a carrier and a carrier carrying effect.

  Preferred examples of the water-soluble polymer compound having a single crosslinkable group include polyallylamine, polyacrylic acid, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, polyethyleneimine, polyvinylamine, polyornithine, polylysine and the like. Most preferred is polyvinyl alcohol. Examples of the water-soluble polymer compound having a plurality of crosslinkable groups include polyvinyl alcohol-polyacrylate copolymer.

  Polyvinyl alcohol is also available as a commercial product, and examples thereof include Poval (manufactured by Kuraray), polyvinyl alcohol (manufactured by Aldrich), and J-Poval (manufactured by Nippon Vinegar Poval). Although there are various molecular weight grades, it is preferable to select one having a weight average molecular weight of 30,000 to 300,000.

  Examples of the polyvinyl alcohol-polyacrylate copolymer include (Kuraray Co., Ltd .: Clastomer AP). There are various molecular weight grades, but it is particularly preferable to use those having a molecular weight of 30,000 to 150,000.

-Crosslinking agent-
The crosslinked structure of the water-soluble polymer compound can be formed by a conventionally known method such as thermal crosslinking, ultraviolet crosslinking, electron beam crosslinking, radiation crosslinking, or photocrosslinking. Photocrosslinking or thermal crosslinking is preferred, and thermal crosslinking is most preferred.
In forming the water-soluble polymer compound layer in the present embodiment, it is preferable to use a composition containing a crosslinking agent together with the water-soluble polymer compound. Hereinafter, the coating composition for forming a polymer compound layer used for forming the polymer compound layer may be simply referred to as “coating solution composition” or “composition”.
As the cross-linking agent, a cross-linking agent formed by selecting and containing a cross-linking agent having two or more functional groups capable of undergoing thermal cross-linking or photo-cross-linking by reacting with the water-soluble polymer having the single or plural cross-linkable groups is formed. The structure needs to be a hydrolysis-resistant crosslinked structure selected from the group (B). From such a viewpoint, as a crosslinking agent that can be used in this embodiment, an epoxy crosslinking agent, a polyvalent glycidyl ether, a polyhydric alcohol, a polyvalent isocyanate, a polyvalent aziridine, a haloepoxy compound, a polyvalent aldehyde, a polyvalent amine, Examples include organometallic crosslinking agents. Preferred are polyvalent aldehydes, organometallic crosslinking agents, and epoxy crosslinking agents, more preferred are organometallic crosslinking agents and epoxy crosslinking agents, and most preferred are glutaraldehyde and formaldehyde having two or more aldehyde groups. It is a polyvalent aldehyde.

A preferable compound as an epoxy crosslinking agent is a compound having two or more epoxy groups, and a compound having four or more epoxy groups is also preferable. Epoxy crosslinking agents are also available as commercial products. For example, Kyoeisha Chemical Co., Ltd., Epolite 100MF (trimethylolpropane triglycidyl ether), Nagase ChemteX Corporation EX-411, EX-313, EX-614B, EX -810, EX-811, EX-821, EX-830, NOF Corporation Epiol E400, etc. are mentioned.
Moreover, as a compound similar to an epoxy crosslinking agent, an oxetane compound having a cyclic ether is also preferably used. The oxetane compound is preferably a polyvalent glycidyl ether having two or more functional groups, and commercially available products include, for example, EX-411, EX-313, EX-614B, EX-810, EX-811, EX manufactured by Nagase ChemteX Corporation. -821, EX-830, and the like.

Hereinafter, other crosslinking agents used for forming a crosslinked structure in the present embodiment will be described.
Examples of the polyvalent glycidyl ether include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether, pentaerythritol polyglycidyl ether, propylene Examples thereof include glycol glycidyl ether and polypropylene glycol diglycidyl ether.

  Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, glycerin, polyglycerin, propylene glycol, diethanolamine, triethanolamine, polyoxypropyl, oxyethyleneoxypropylene block copolymer , Pentaerythritol, sorbitol and the like.

  Examples of the polyvalent isocyanate include 2,4-toluylene diisocyanate and hexamethylene diisocyanate. Examples of the polyvalent aziridine include 2,2-bishydroxymethylbutanol-tris [3- (1-acylidinyl) propionate], 1,6-hexamethylenediethyleneurea, diphenylmethane-bis-4,4′-. N, N′-diethylene urea and the like can be mentioned.

Examples of the haloepoxy compound include epichlorohydrin and α-methylchlorohydrin.
Examples of the polyvalent aldehyde include glutaraldehyde and glyoxal.
Examples of the polyvalent amine include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and polyethyleneimine.
Examples of organometallic crosslinking agents include organic titanium crosslinking agents and organic zirconia crosslinking agents.

Among the above crosslinking agents, for example, when a high molecular weight polyvinyl alcohol having a weight average molecular weight of 130,000 or more is used as the water soluble polymer compound, the reactivity with the water soluble polymer compound is good, and the hydrolysis resistance is high. In particular, an epoxy compound and glutaraldehyde are particularly preferable because an excellent crosslinked structure can be formed.
In addition, for example, when using polyallylamine having a weight average molecular weight of 10,000 or more, it is possible to form a crosslinked structure having good reactivity with this water-soluble polymer compound and excellent hydrolysis resistance. Epoxy compounds, glutaraldehyde, and organometallic crosslinking agents are particularly preferred.
When polyethyleneimine or polyallylamine is used as the water-soluble polymer compound, an epoxy compound is particularly preferable as the crosslinking agent.

When the coating liquid composition for forming a water-soluble polymer compound layer contains a cross-linking agent, the water-soluble polymer compound has a cross-linked structure when the water-soluble polymer compound has a crosslinkable group. It is preferably a crosslinked structure formed by reacting 0.001 mol to 80 mol of a crosslinking agent with respect to 100 mol of the crosslinkable group. When the content is in the above range, the formability of the crosslinked structure is good and the shape maintaining property of the formed gel film is excellent.

-Career-
The carrier is various water-soluble inorganic substances having affinity with carbon dioxide gas (for example, carbon dioxide gas) and showing basicity. In this embodiment, the alkali metal carbonate, alkali metal bicarbonate, And selected from alkali metal hydroxides. Here, as the alkali metal, an alkali metal element selected from cesium, rubidium, potassium, lithium, and sodium is preferably used.

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, a compound containing potassium, rubidium, or cesium as an alkali metal element is preferable from the viewpoint of good affinity with carbon dioxide gas. A compound containing potassium, rubidium, and cesium as alkali metal elements is also preferable. The carrier may be a single carrier or a combination of a plurality of types.

-Other ingredients-
In addition to the water-soluble polymer compound, the crosslinking agent, and the carbon dioxide carrier, various additives may be used in combination in the composition used for forming the water-soluble polymer compound layer (facilitated transport film 38A). Further, water as a solvent may be contained although it is dried at the time of production and is in a small amount.

  For example, a reaction promoting additive may be mentioned, and it is preferable to use a nitrogen-containing compound or sulfur oxide which is a reaction promoting additive for the purpose of promoting the reaction between the acidic gas and the carrier.

Examples of nitrogen-containing compounds include amino acids such as glycine, alanine, serine, proline, histidine, taurine, and diaminopropionic acid, hetero compounds such as pyridine, histidine, piperazine, imidazole, and triazine, monoethanolamine, diethanolamine, and triazine. Alkanolamines such as ethanolamine, monopropanolamine, dipropanolamine, tripropanolamine, cyclic polyetheramines such as cryptand [2.1] and cryptand [2.2], cryptand [2.2.1] Bicyclic polyetheramines such as cryptand [2.2.2], porphyrin, phthalocyanine, ethylenediaminetetraacetic acid and the like can be used.
As the sulfur compound, for example, amino acids such as cystine and cysteine, polythiophene, dodecylthiol and the like can be used.

  Other examples include surfactants and set agents. Examples of the surfactant include the following.

-1. Anionic surfactant
(Carboxylic acid type)
・ Sodium octanoate (C ₇ H ₁₅ COONa)
・ Sodium decanoate (C ₉ H ₁₉ COONa)
・ Sodium laurate (C ₁₁ H ₂₃ COONa)
・ Myristate sodium (C ₁₃ H ₂₇ COONa)
・ Sodium palmitate (C ₁₅ H ₃₁ COONa)
・ Sodium stearate (C ₁₇ H ₃₅ COONa, w: Sodium stearate)
・ PFOA (C ₇ F ₁₅ COOH)
・ Perfluorononanoic acid (C ₈ F ₁₇ COOH, w: Perfluorononanoic acid)
· N-lauroyl sarcosine sodium _{(C 11 H 23 CON (CH} 3) CH 2 COONa, w: Sodium lauroyl sarcosinate)
・ Sodium cocoyl glutamate (HOOCCH ₂ CH ₂ CH (NHCOR) COONa [R: alkyl having 11 to 17 carbon atoms])
・ Alpha sulfo fatty acid methyl ester salt (CH ₃ (CH ₂ ) _n CH (SO ₃ Na) COOCH ₃ [n = 1-19])
(Sulfonic acid type)
・ Sodium 1-hexanesulfonate (C ₆ H ₁₃ SO ₃ Na)
・ Sodium 1-octanesulfonate (C ₈ H ₁₇ SO ₃ Na)
・ Sodium 1-decanesulfonate (C ₁₀ H ₂₁ SO ₃ Na)
・ Sodium 1-dodecanesulfonate (C ₁₂ H ₂₅ SO ₃ Na)
・ Perfluorobutanesulfonic acid (C ₄ F ₉ SO ₃ H, w: Perfluorobutanesulfonic acid)
・ Sodium linear alkylbenzenesulfonate (RC ₆ H ₄ SO ₃ Na [R: alkyl having 3 to 20 carbon atoms])
・ Sodium toluene sulfonate (CH ₃ C ₆ H ₄ SO ₃ Na)
・ Sodium cumene sulfonate (C ₃ H ₇ C ₆ H ₄ SO ₃ Na)
・ Sodium octylbenzenesulfonate (C ₈ H ₁₇ C ₆ H ₄ SO ₃ Na)
· Sodium dodecylbenzenesulfonate _{(DBS; C 12 H 25 C} 6 H 4 SO 3 Na)
・ Naphthalene sodium sulfonate (C ₁₀ H ₇ SO ₃ Na)
・ Naphthalenedisulfonic acid disodium (C ₁₀ H ₆ (SO ₃ Na) ₂ )
・ Trisodium naphthalene trisulfonate (C ₁₀ H ₅ (SO ₃ Na) ₃ )
・ Sodium butyl naphthalenesulfonate (C ₄ H ₉ C ₁₀ H ₆ SO ₃ Na)
・ Sodium di (2-ethylhexyl) sulfosuccinate (the following compound; Lapisol A-90, manufactured by NOF Corporation)

(Sulfate type)
・ Sodium lauryl sulfate (C ₁₂ H ₂₅ OSO ₃ Na)
・ Sodium myristyl sulfate (C ₁₄ H ₂₉ OSO ₃ Na)
・ Sodium laureth sulfate (C ₁₂ H ₂₅ (CH ₂ CH ₂ O) _n OSO ₃ Na, w: Sodium laureth sulfate)
・ Sodium polyoxyethylene alkylphenol sulfonate (C ₈ H ₁₇ C ₆ H ₄ O [CH ₂ CH ₂ O] ₃ SO ₃ Na)
・ Ammonium lauryl sulfate (C ₁₂ H ₂₅ OSO ₃ NH ₄ , w: Ammonium lauryl sulfate)
(Phosphate ester type)
・ Lauryl phosphate (C ₁₂ H ₂₅ OPO (OH) ₂ )
・ Sodium lauryl phosphate (C ₁₂ H ₂₅ OPOOHONa)
・ Potassium lauryl phosphate (C ₁₂ H ₂₅ OPOOHOK)

-2. 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 + (CH 3) 3 Br)
・ Benzyltrimethylammonium chloride (C ₆ H ₅ CH ₂ N ⁺ (CH ₃ ) ₃ Cl)
・ Benzyltriethylammonium chloride (C ₆ H ₅ CH ₂ N ⁺ (C ₂ H ₅ ) ₃ Cl)
・ Benzalkonium chloride (C ₆ H ₅ CH ₂ N ⁺ (CH ₃ ) ₂ RCl [R: alkyl having 8 to 17 carbon atoms])
Benzalkonium bromide (C ₆ H ₅ CH ₂ N ⁺ (CH ₃ ) ₂ RBr [R: alkyl having 8 to 17 carbon atoms])
・ Benzethonium chloride (C ₆ H ₅ CH ₂ N ⁺ (CH ₃ ) ₂ (CH ₂ CH ₂ O) ₂ C ₆ H ₄ C ₈ H ₁₇ Cl)
・ Dialkyldimethylammonium chloride (RN ⁺ R (CH ₃ ) ₂ Cl [R: alkyl having 3 to 20 carbon atoms])
・ Didecyldimethylammonium chloride (C ₁₀ H ₂₁ N ⁺ C ₁₀ H ₂₁ (CH ₃ ) ₂ Cl)
・ Distearyldimethylammonium chloride (C ₁₈ H ₃₇ N ⁺ C ₁₈ H ₃₇ (CH ₃ ) ₂ Cl, w: Dimethyldioctadecylammonium chloride)
(Alkylamine salt type)
・ Monomethylamine hydrochloride (CH ₃ NH ₂ · HCl)
・ Dimethylamine hydrochloride ((CH ₃ ) ₂ NH · HCl)
・ Trimethylamine hydrochloride ((CH ₃ ) ₃ N · HCl)
(Substance having a pyridine ring)
・ Butylpyridinium chloride (C ₅ H ₅ N ⁺ C ₄ H ₉ Cl)
・ Dodecylpyridinium chloride (C ₅ H ₅ N ⁺ C ₁₂ H ₂₅ Cl)
・ Cetylpyridinium chloride (C ₅ H ₅ N ⁺ C ₁₆ H ₃₃ Cl)

-3. Nonionic surfactant
(Ester type)
Lauric glyceryl _{(C 11 H 23 COOCH 2 CH} (OH) CH 2 OH, w: Glyceryl laurate)
· Glyceryl 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)
-Octaethylene glycol monododecyl ether (C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₈ H, w: Octaethylene glycol monododecyl ether)
・ Polyoxyethylene alkyl phenyl ether (RC ₆ H ₄ O (CH ₂ CH ₂ O) _n H [R: alkyl having 3 to 20 carbon atoms])
- Nonoxynol _{(C 9 H 19 C 6 H} 4 O (CH 2 CH 2 O) nH, w: Nonoxynols)
- Nonoxynol _{-9 (C 9 H 19 C 6} H 4 O (CH 2 CH 2 O) 9 H, w: Nonoxynol-9)
・ Polyoxyethylene polyoxypropylene glycol (H (OCH ₂ CH ₂ ) _l (OC ₃ H ₆ ) _m (OCH ₂ CH ₂ ) _n OH)
(Ester ether type)
・ Polyoxyethylene sorbitan fatty acid ester ・ Polyoxyethylene hexitan fatty acid ester ・ Sorbitan fatty acid ester polyethylene glycol (alkanolamide type)
・ Lauric acid diethanolamide (C ₁₁ H ₂₃ CON (C ₂ H ₄ OH) ₂ )
・ Oleic acid diethanolamide (C ₁₇ H ₃₃ CON (C ₂ H ₄ OH) ₂ )
・ Stearic acid diethanolamide (C ₁₇ H ₃₅ CON (C ₂ H ₄ OH) ₂ )
・ Cocamide DEA (CH ₃ (CH ₂ ) _n CON (C ₂ H ₄ OH) ₂ , w: Cocamide DEA)
(Alkyl glycoside)
・ Octyl glucoside (C ₈ H ₁₇ C ₆ H ₁₁ O ₆ )
Decyl glucoside (C ₁₀ H ₂₁ C ₆ H ₁₁ O ₆ , w: Decyl glucoside)
・ Lauryl glucoside (C ₁₂ H ₂₅ C ₆ H ₁₁ O ₆ , w: Lauryl glucoside)
(Higher alcohol)
・ Cetanol (C ₁₆ H ₃₃ OH, w: Cetyl alcohol)
・ Stearyl alcohol (C ₁₈ H ₃₇ OH, w: Stearyl alcohol)
・ Oleyl alcohol (CH ₃ (CH ₂ ) ₇ CH = CH (CH ₂ ) ₈ OH, w: Oleyl alcohol)

-4. 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 CHOHCH ₂ SO ₃ ⁻ )
(Alkylimidazole type)
- 2-alkyl -N- carboxymethyl -N- hydroxyethyl imidazolinium betaine _{(RC 3 H 4 N 2 (} C 2 H 4 OH) CH 2 COO - [R: alkyl having 3 to 20 carbon atoms])
(Amino acid type)
・ Lauroyl glutamate sodium (C ₁₁ H ₂₃ CON (C ₂ H ₄ COOH) HCHCOONa)
- lauroyl potassium glutamate _{(C 11 H 23 CON (C} 2 H 4 COOH) HCHCOOK)
・ Lauroylmethyl-β-alanine (C ₁₁ H ₂₃ CONH (C ₂ H ₄ COOCH ₃ )
(Amine oxide type)
Lauryl dimethylamine -N- oxide ^{_{(C 12 H 25 N + (}} CH 3) 2 O -)
· Oleyl dimethylamine -N- oxide ^{_{(C 18 H 37 N + (}} CH 3) 2 O -)

Examples of the set agent include agar (Inagar Industry: UP-37) and gelatin (Nitta Gelatin). In addition, you may contain antioxidant, unless the effect of this embodiment is impaired. The addition of an antioxidant has the advantage of further improving wet heat resistance.
Commercially available products may be used as the antioxidant, and suitable antioxidants include, for example, dibutylhydroxytoluene (BHT), Irganox 1010, Irganox 1035FF, Irganox 565, and the like.

(Porous support)
The porous support 38B that constitutes the carbon dioxide separation layer 38 together with the facilitated transport film 38A has heat resistance, like the facilitated transport film 38A.
As the material of the porous support 38B, the same material as the supply gas flow path member 36 can be used.

(Permeate gas channel member)
The permeating gas flow path member 40 that constitutes the laminate 16 together with the carbon dioxide separation layer 38 is a member that guides the carbon dioxide 24 that has reacted with the carrier and permeated the carbon dioxide separation layer 38 toward the through-hole group 14B. . The permeate gas flow path member 40 has a function as a spacer, and has a function of flowing the permeated carbon dioxide gas 24 to the inside of the permeate gas flow path member 40. Further, adhesive portions 42 and 40 described later are provided. Like the supply gas flow path member 36, the permeate gas flow path member 40 is preferably a net-like member so as to have a permeating function. The material of the permeate gas flow path member 40 can be the same as that of the supply gas flow path member 36.

(Adhesive part)
The bonding portion 42 and the bonding portion 44 bond the carbon dioxide separation layer 38 and the permeating gas flow path member 40 in a state where the laminate 16 is wound around the central tube 14 in the direction of arrow C in the drawing. Further, the bonding portion 42 bonds the carbon dioxide separation layer 38 and the permeating gas channel member 40 before the laminate 16 is wound around the central tube 14. The material of the bonding part 42 and the bonding part 44 is not particularly limited as long as it has heat and humidity resistance. For example, epoxy resin, vinyl chloride copolymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinylidene chloride. Copolymer, vinyl chloride-acrylonitrile copolymer, butadiene-acrylonitrile copolymer, polyamide resin, polyvinyl butyral, polyester, cellulose derivative (nitrocellulose, etc.), styrene-butadiene copolymer, various synthetic rubber resins, phenol Examples include resins, urea resins, melamine resins, phenoxy resins, silicon resins, urea formamide resins, and the like.

  Both the bonding portion 42 and the bonding portion 44 include circumferential bonding portions 42A and 44A that bond the carbon gas separation layer 38 and the end portions on both sides of the permeating gas channel member 40 along the circumferential direction of the central tube 14, and carbon dioxide gas. The separation layer 38 and axially bonded portions 42B and 44B for bonding the circumferential end portions of the permeate gas flow path member 40 are provided.

  The circumferential adhesive portion 42A and the axial adhesive portion 42B are connected to each other, and the so-called “envelope” in which the circumferential end portion between the carbon dioxide gas separation layer 38 and the permeating gas flow path member 40 at the beginning of winding is opened as the adhesive portion 42 as a whole. "". A partition adhesive portion 50 is formed between the circumferential adhesive portions 42A and on the outer peripheral side of the partition member 34 along the circumferential direction (the length direction of the laminate 16 before winding). The partition bonding portion 50 is not in contact with the axial direction bonding portion 42B, and the carbon dioxide gas 24 that has passed through the carbon dioxide separation layer 38 is caused by the sweep gas 28 between the circumferential direction bonding portion 42A and the axial direction bonding portion 42B. A flow path P1 flowing to the through hole group 14B is formed.

  Similarly, the circumferential adhesive portion 44A and the axial adhesive portion 44B are connected to each other, and the circumferential end portion between the carbon dioxide separation layer 38 and the permeate gas flow path member 40 at the beginning of winding is opened as the entire adhesive portion 44. It is a so-called “envelope shape”. Further, partition adhesive portions 52 are formed between the circumferential adhesive portions 44A and on the outer peripheral side of the partition member 34 along the circumferential direction (the length direction of the laminated body 16 before winding). The partition bonding portion 52 is not in contact with the axial direction bonding portion 44B, and the carbon dioxide gas 24 that has permeated the carbon dioxide separation layer 38 is caused by the sweep gas 28 between the circumferential direction bonding portion 44A and the axial direction bonding portion 42B. A flow path P2 flowing to the through hole group 14B is formed.

<Manufacturing method of separation module>
Next, a method for manufacturing the separation module 10 according to the embodiment of the present invention will be described.

  3A to 3C are a series of process diagrams showing a method for manufacturing the separation module 10 according to the embodiment of the present invention.

  First, as shown in FIG. 3A, a step of preparing a central tube 14 in which a plurality (three in this embodiment) of through-hole groups 14B are formed is performed.

  Next, as shown in FIG. 3B, a step of attaching a plurality of (three sets in this embodiment) center tube 14 to the pair of telescope prevention plates 20 is performed. In this step, a pair of telescope prevention plates 20 are attached so as to sandwich one through-hole group 14B and not to interfere when the laminated body 16 is wound around the central tube 14 later.

  Next, a step of simultaneously forming a plurality of separation module units 12 is performed. In this step, as shown in FIG. 3C, the tips of the plurality of laminates 16 are fixed to the central tube 14 with a fixing member (not shown) such as Kapton tape or adhesive, and the central tube 14 is moved around the tube axis. A plurality of laminated bodies 16 are wound around the central tube 14 simultaneously while rotating.

  Through the above manufacturing steps, a separation module 10 according to the embodiment of the present invention as shown in FIG. 1 can be obtained.

<Action>
Next, the operation of the separation module according to the reference example of the present embodiment will be described.

  FIG. 7 is a perspective view in which a part of the separation module according to the reference example of the present embodiment is provided.

  As shown in FIG. 7, unlike the present embodiment, the separation module 100 has only one separation module unit. That is, the separation module 100 can be identified with the separation module unit, and includes a tube body 102 having a through hole group 102A and a laminated body 104 wound around the tube body 102 so as to cover the through hole group 102A. Yes. A plurality of separation modules 100 are housed in a pressure vessel (not shown) during use, and the tubes 102 of the separation module 100 are connected to each other by a clamp 106.

  According to the configuration of the separation module 100 according to this reference example, the carbon dioxide gas can be sequentially separated from the raw material gas by the plurality of separation modules 100, but pressure loss occurs at the connection portion between the separation modules 100. End up. Further, when stored in the pressure vessel, when the clamp connection is made in the pressure vessel, the separation module is damaged, and there is a problem that the separation performance is remarkably lowered.

  Next, the operation of the separation module 10 according to this embodiment will be described.

  According to the configuration of the separation module 10 according to the present embodiment, as shown in FIG. 1, the separation module 10 is stored in the pressure vessel alone at the time of use, and is separated on one end side in the tube axis direction A among the plurality of separation module units 12. When the raw material gas 22 flows into the laminate 16 of the module unit 12, the carbon dioxide gas 24, which is a component of the raw material gas 22, is separated and guided to the through hole group 14B by the facilitated transport film 38A as a separation film. The remaining gas 26 that has been separated is sequentially introduced to the stacked body 16 of the separation module unit 12 on the other end side in the tube axis direction A, and the components are separated. The components separated from each stacked body 16 flow from the stacked bodies 16 to the central tube 14 through the through-hole group 14B that each covers. Thus, since the central tube 14 is common to the plurality of laminated bodies 16, that is, the plurality of separation module units 12, the separation module of the reference example having the tubular body 102 for each separation module unit (laminated body 104). Compared with 100, there is no need to connect the central tubes 14 to each other, and pressure loss can be suppressed. Therefore, the separation module has a highly efficient separation ability.

As an alternative to connecting the separation modules 100 of the reference example, it is conceivable to simply lengthen the entire separation module 100 in the tube axis direction A. However, since it is difficult to lengthen the laminated transport 104 from the viewpoint of making the physical properties of the facilitated transport film 38A uniform and the viewpoint of manufacturing, the separation module 10 according to the present embodiment is effectively used as a substitute for the reference example.
Note that the separation module 10 of the present embodiment may be placed in a plurality of pressure vessels instead of a single separation module 10. Even in this case, as a result of the reduction in the number of clamp connections, it becomes easy to align the axes, and the separation module 10 can be prevented from being broken (leakage is caused). Further, as a result of the reduction in the number of clamp connections, the clamp connection is facilitated.

  In addition, each separation module unit 12 of the separation module 10 according to the present embodiment includes a plurality of partition members 34, adhesive portions 42 and 44, and partition adhesive portions 50 and 52. For this reason, when the sweep gas 28 flows into the center tube 14 from the inlet 30, it hits the plurality of partition members 34, flows out from the center tube 14 through the through hole group 14 </ b> B, and flows into the laminate 16. Pass through P2. At this time, the sweep gas 28 again flows into the center tube 14 over the partition member 34 while sweeping the carbon dioxide gas 24 separated by the facilitated transport film 38A. Thereby, the separated carbon dioxide gas 24 flows into the central tube 14 through the through hole group 14 </ b> B without staying in the stacked body 16, and flows out from the outlet 32 together with the sweep gas 28. As a result, leakage of the carbon dioxide gas 24 is suppressed, and the separation performance is increased.

  In addition, the plurality of separation module units 12 have both ends of the laminate 16 fitted in the telescope prevention plate 20. For this reason, the winding shift | offset | difference of all the laminated bodies 16 is prevented.

  Moreover, in the manufacturing method of the separation module 10 which concerns on embodiment of this invention, since it has the process of winding the laminated body 16 around the center pipe | tube 14 simultaneously, production speed increases. Moreover, the dispersion | variation (winding diameter etc.) between the laminated bodies 16 can be suppressed, and the dispersion | variation in performance can be suppressed.

<Modification>
Although the present invention has been described in detail with respect to a plurality of embodiments, the present invention is not limited to such embodiments, and various other embodiments are possible within the scope of the present invention. It is clear to the contractor. Moreover, the above-mentioned embodiment and the following modified example can be implemented in combination as appropriate.

  Although the case where the partition member 34 and the partition bonding parts 50 and 52 are provided has been described in the above embodiment, these may be omitted. In this case, one end of the tube is closed and the sweep gas 28 does not flow.

  In the above embodiment, the case where the laminated body 16 is wound around the central tube 14 at the same time when the separation module 10 is manufactured has been described. However, the laminated body 16 may be wound around the central tube 14 separately. .

  Moreover, although the case where the facilitated transport type facilitated transport film 38A is used as the separation membrane has been described in the above embodiment, other separation membranes may be used. Examples of other separation membranes include molecular gate type membranes composed of dendrimers and the like, dissolution diffusion type membranes, Knudsen diffusion type membranes, molecular sieve type membranes, surface diffusion type membranes, and the like. Further, it can be applied to a module of a polyamide-based liquid separation membrane.

  The constituent elements of the source gas 22 separated by the separation membrane are not limited to the carbon dioxide gas 24, and may be fluids such as other gases such as hydrogen or liquids such as water.

  Moreover, what flows into the laminated body 16 is not limited to the raw material gas 22, and may be a fluid such as a liquid.

  Moreover, although the case where the acidic gas 24 was discharged | emitted in the same direction as the inflow direction (the discharge direction is also the same direction) of the raw material gas 22 was demonstrated, you may discharge | emit in the direction opposite to the inflow direction of the raw material gas 22. In this case, the sweep gas 28 is also introduced from the direction opposite to the inflow direction of the source gas 22.

Moreover, you may replace the telescope prevention plate 20 mentioned above with the telescope prevention plate 60 as shown to FIG. 4A and 4B.
The telescope prevention plate 60 is divided into two along the axial direction of the cylindrical portion 62 into which the central tube 14 is inserted. The telescoping prevention plate 60 when integrated is a cylindrical portion 62, a spoke portion 64 that extends radially from the outer peripheral surface of the cylindrical portion 62 and abuts against the end surface of the laminated body 16, and a tip portion of the spoke portion 64. And a cap portion 66 that protrudes to both sides along the tube axis direction A (the axial direction of the cylindrical portion 62) and is fitted to the outer peripheral portion of the end portion of the adjacent laminate 16.

Further, the telescope prevention plate 60 is provided with connection means 68 and 70 connected to each other. Although the connection means 68 and 70 are not particularly limited, a locking tool, an adhesive, a fitting member, or the like can be used. In FIG. 4A and FIG. 4B, a locking tool is used as the connecting means 68 and 70.
The connection means 68 shown in FIGS. 4A and 4B includes a support portion 68A provided at one end portion of the inner peripheral surface of one of the divided cap portions 66, and a hook portion 68B rotatably supported by the support portion 68A. ,have. Further, the connecting means 68 has a hook portion 68C that is provided at one end portion of the inner peripheral surface of the other divided cap portion 66 and that hooks 68B are hooked on.
4A and 4B includes a hook portion 70A provided at one end of the inner peripheral surface of one divided cap portion 66 and an inner peripheral surface of one divided cap portion 66. And a claw portion 70B that protrudes from the inner peripheral surface in the inner peripheral direction and is hooked on the hook portion 70A.

  According to the configuration of the telescope prevention plate 60 described above, as shown in FIG. 5, adjacent laminates 16 can use one telescope prevention plate 60 in common.

  Further, since the telescope prevention plate 60 is divided, it is easy to fit the cap portion 66 into the outer peripheral portion of the end portion between the adjacent stacked bodies 16. However, the telescope prevention plate 60 may not be divided as long as the adjacent stacked bodies 16 are used in common. Further, the connecting means 68 and 70 may be provided not on the inner peripheral surface of the cap portion 66 but on the outer peripheral surface. However, it is preferable to provide it on the inner peripheral surface from the viewpoint of not obstructing when the O-ring is attached to the outer peripheral surface.

Moreover, although the case where the center tube 14 as shown to FIG. 3A was used was demonstrated in the said embodiment, you may use the center tube 80 as shown in FIG.
The center tube 80 includes a plurality of through-hole groups 14 </ b> B and marks 82 as positioning means for positioning the laminated body 16. As described above, since the central tube 80 has the mark 82, a plurality of stacked bodies can be accurately wound around the tube. As the positioning means, in addition to the mark 82, the central tube 80 may be provided with a concave portion or a convex portion.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited and interpreted by these Examples at all.

<Example 1>
A telescope prevention plate was attached to a central tube having a plurality of through-hole groups as shown in FIG. 3A, and then a tricot knitted epoxy-impregnated polyester permeating gas channel member was fixed to the central tube. Thereafter, a PTFE porous support with polypropylene support material (EXPG, manufactured by GE Energy Co., Ltd.) coated with a hydrogel film composed of a water-soluble polymer compound, carbon dioxide carrier, glutaraldehyde and a surfactant was folded in half to 0.5 mm. A polypropylene net was sandwiched inside. The porous support is coated with a high-viscosity (about 40 cp) epoxy adhesive (E120HP, manufactured by Henkel Japan Co., Ltd.) on the permeate gas channel member, and a tricot knitted epoxy-containing polyester permeate gas channel material is stacked. These laminates were wrapped around the central tube in multiple layers so as to cover one through hole group. Next, the laminated body is wound around the adjacent through-hole group in the same manner, and the telescope prevention plates are attached to both ends of the laminated body, so that one central tube has three separation module units according to the first embodiment. A separation module was produced.

<Example 2>
The same laminate as in Example 1 was wound around the central tube, but a common telescope prevention plate as shown in FIGS. 4A, 4B, and 5 was used between adjacent separation module units.
In this way, the number of telescope prevention plates is usually reduced to 4 where 6 are required when 3 laminates are wound, and there are 3 separation module units in one central tube. A separation module according to 2 was produced.

<Example 3>
Three separation module units were produced in one central tube using the same laminate as in Example 1, but three were produced at a time rather than one by one. Specifically, the separation tube according to Example 3 was manufactured by rotating the central tube around the axis and simultaneously winding the three laminated bodies around the central tube.

<Comparative Example 1>
A tricot-knitted epoxy-impregnated polyester permeated gas passage member was fixed to the central tube using a central tube having only one through hole group. After that, a PTFE porous support with polypropylene support material (GE Energy, EXPG) coated with a hydrogel film composed of a water-absorbing polymer, carbon dioxide carrier, glutaraldehyde, and a surfactant was folded in half and made into 0.5 mm polypropylene. I put the net inside. The porous support is coated with a high-viscosity (about 40 cp) epoxy adhesive (E120HP, manufactured by Henkel Japan Co., Ltd.) on the permeate gas channel member, and a tricot knitted epoxy-containing polyester permeate gas channel material is stacked. A module unit was produced by wrapping around the central tube in multiple layers. A plurality of module units were produced in the same manner as described above, and the central tubes of the module units were connected by clamps. Further, a telescoping prevention plate was attached to the module unit at the end, and a separation module unit according to Comparative Example 1 was produced.

<Evaluation>
The produced separation modules according to Examples 1 to 3 and Comparative Example 1 were put in pressure vessels, respectively, and the acid gas separation performance was evaluated under the following condition 1.

-Condition 1-
As a test gas, a source gas (flow rate: 2.2 L / min) of H ₂ : CO ₂ : H ₂ O = 45: 5: 50 is supplied to the separation module at a temperature of 130 ° C. and a total pressure of 301.3 kPa. Ar gas (flow rate 0.6 L / min) was flowed as a sweep gas. The permeated gas was analyzed with a gas chromatograph, and the CO ₂ permeation rate (P (CO ₂ )) and the CO ₂ / H ₂ separation factor (α) were calculated. The calculation results of P (CO ₂ ) and α are summarized in Table 1 below.

As shown in Table 1, the separation modules according to Examples 1 to 3 had better values of the CO ₂ permeation rate and the CO ₂ / H ₂ separation coefficient than the separation module according to Comparative Example 1. This is probably because the separation modules according to Examples 1 to 3 have no place for connecting the central tubes to each other, and thus pressure loss at the place is suppressed.

<Example 4>
Next, a separation module according to Example 4 was produced in exactly the same manner as in Example 1 except that a polyimide membrane was applied instead of the hydrogel membrane consisting of the water-absorbing polymer, carbon dioxide carrier, glutaraldehyde, and surfactant. did.

<Comparative example 2>
A separation module according to Comparative Example 2 was produced in exactly the same manner as in Comparative Example 1, except that a polyimide membrane was applied instead of the hydrogel membrane composed of the water-absorbing polymer, carbon dioxide carrier, glutaraldehyde, and surfactant.

<Evaluation>
The produced separation modules according to Example 4 and Comparative Example 2 were put in pressure vessels, respectively, and acid gas separation performance was evaluated under the following condition 2.

-Condition 2-
As a test gas, CH ₄ : CO ₂ = 50: 50 source gas (flow rate: 2.2 L / min) at a temperature of 40 ° C. and a total pressure of 301.3 kPa, each acidic gas is supplied to the separation module, and a sweep gas on the permeate side Ar gas (flow rate 0.6 L / min) was allowed to flow. The permeated gas was analyzed with a gas chromatograph, and the CO ₂ permeation rate (P (CO ₂ )) and the CO ₂ / H ₂ separation factor (α) were calculated. The calculation results of P (CO ₂ ) and α are summarized in Table 2 below.

As shown in Table 2, the separation module according to Example 4 had better values for the CO ₂ permeation rate and the CO ₂ / H ₂ separation coefficient than the separation module according to Comparative Example 2. This is probably because the separation module according to Example 4 does not have a place where the central tubes are connected to each other, and therefore pressure loss at the place is suppressed.

<Example 5>
Next, instead of the PTFE porous support with a polypropylene support coated with a hydrogel membrane comprising a water-soluble polymer compound, carbon dioxide carrier, glutaraldehyde, and a surfactant in Example 1, the support and the separation membrane were as follows. A separation module according to Example 5 was produced in exactly the same manner as in Example 1 except that the above was used.

-Support-
On a polyester nonwoven fabric (manufactured by Hirose Paper Co., Ltd.), a polysulfone concentration 15 wt% solution of dimethylformamide solvent was cast to a layer thickness of 200 μm, and immediately immersed in water to prepare a polysulfone porous support.

-Separation membrane-
The polysulfone support produced by the above method was immersed in a 3.4 wt% aqueous solution of metaphenylenediamine for 2 minutes, the support membrane was pulled up, and after removing the excess aqueous solution, n-containing 0.175 wt% of trimesic acid chloride. The decane solution was applied so that the support surface was completely wetted. Furthermore, it washed with 90 degreeC hot water, and obtained the composite reverse osmosis membrane.

<Comparative Example 3>
Except that a module group including a composite reverse osmosis membrane was produced in the same manner as in Example 5 instead of the hydrogel membrane comprising a water-absorbing polymer, carbon dioxide carrier, glutaraldehyde, and a surfactant in Comparative Example 1. A separation module according to Comparative Example 3 was produced by the same method.
<Evaluation>
Regarding the characteristics of the separation membrane module according to Example 5 and Comparative Example 3, seawater (TDS (Total Dissolved Solids) concentration of about 3.5%, boron concentration of about 5.0 ppm was adjusted to a separation membrane module at a temperature of 25 ° C. and a pH of 6.5. ) Was supplied at an operating pressure of 5.5 MPa, membrane filtration was performed, and the quality of the permeated water and the feed water was measured, and the following formula was obtained.

(TDS removal rate)
TDS removal rate (%) = 100 × {1− (TDS concentration in permeated water / TDS concentration in feed water)}

(Membrane permeation flux)
Membrane permeation flux (m ³ / m ² / day) was expressed in terms of the permeation amount of the feed water (seawater) per square meter of the membrane surface with the permeation amount per day (cubic meter). The results of TDS removal rates and membrane permeation flow rates calculated for the separation modules according to Example 5 and Comparative Example 3 are summarized in Table 3 below.

  As shown in Table 3, the separation module according to Example 5 had better TDS removal rate and permeation flow rate values than the separation module according to Comparative Example 3. This is probably because the separation module according to Example 5 does not have a place where the central tubes are connected to each other, and therefore pressure loss at the place is suppressed.

DESCRIPTION OF SYMBOLS 10 Separation module 14 Tube 14A Outer peripheral surface 14B Through-hole group 14 and 80 Center pipe (tube)
16 Laminated body 20, 60 Telescope prevention plate (winding prevention member)
20A, 62 Tube part 20B, 64 Spoke part 20C, 66 Cap part 22 Source gas (gas)
24 Carbon dioxide (gas component)
28 Sweep gas 30 Inlet 32 Outlet 34 Partition member 38A Accelerated transport membrane (component of separation membrane)
38B Porous support (component of separation membrane)
68, 70 Connection means 82 Mark (positioning means)

Claims (12)

A tube body in which a plurality of through-hole groups are formed on the outer peripheral surface at intervals in the tube axis direction;
A separation membrane that separates a liquid or gas component and guides it to the through-hole group; covers each of the plurality of through-hole groups; Or a plurality of laminates into which the gas flows,
A separation module. The separation membrane is a facilitated transport type membrane,
The separation module according to claim 1. The separation membrane has a facilitated transport membrane containing a water-soluble polymer compound and a carbon dioxide carrier, and a porous support that supports the facilitated transport membrane.
The separation module according to claim 2. The separation membrane is a molecular gate type membrane,
The separation module according to claim 1. Having a plurality of winding deviation preventing members fitted into both ends of the laminated body and preventing winding deviation of the laminated body;
The separation module according to any one of claims 1 to 4. The tube includes an inlet through which a sweep gas is introduced, an outlet through which the gas separated from the separation membrane and collected from the through-hole group through the laminated body flows out together with the sweep gas, and each through-hole group A plurality of partition members that are located in a central portion in the tube axis direction and partition the inside of the tube body,
The separation module according to any one of claims 1 to 5. The winding deviation prevention member is
A cylindrical portion into which the tubular body is inserted;
A spoke portion that extends radially from the outer peripheral surface of the cylindrical portion and contacts the end surface of the laminate;
Cap portions that are provided at the tip portions of the spoke portions, project to both sides along the tube axis direction, and are fitted into the outer peripheral portions of the end portions of the adjacent laminates,
The separation module according to claim 5. The winding deviation prevention member is divided along the axial direction of the cylindrical portion,
The divided winding deviation prevention member is provided with connection means connected to each other.
The separation module according to claim 7. The tubular body has positioning means for wrapping the laminated body.
The separation module according to any one of claims 1 to 8. A manufacturing method for manufacturing the separation module according to any one of claims 1 to 9,
A method for manufacturing a separation module, the method comprising a step of rotating the tube body around an axis and winding the plurality of laminated bodies around the tube body simultaneously.   A tubular body that is used in the separation module according to any one of claims 1 to 9, and has a plurality of through-hole groups on an outer peripheral surface at intervals in the tube axis direction. An anti-winding member used in the separation module according to claim 7,
A cylindrical portion into which the tubular body is inserted;
A spoke portion that extends radially from the outer peripheral surface of the cylindrical portion and contacts the end surface of the laminate;
Cap portions that are provided at the tip portions of the spoke portions, project to both sides along the tube axis direction, and are fitted into the outer peripheral portions of the end portions of the adjacent laminates,
An anti-winding member having