JP6577898B2 - Liquid mixture supply jig and method of manufacturing separation membrane structure using the same - Google Patents

Description

  The present invention relates to a liquid mixture supply jig and a method for producing a separation membrane structure using the same.

  Conventionally, a flow-down method is known as a technique for forming a porous film on the inner surface of one or more through holes provided in a porous body (see, for example, Patent Document 1). The flow-down method is a method in which a liquid mixture is poured into one or more through holes using a funnel fixed to the upper end of a porous body.

JP 2009-189941 A

  However, when the liquid mixture is poured using a funnel, it is difficult to uniformly supply the liquid mixture to the porous body, and thus the film thickness of the porous film tends to be uneven on the inner surface of the through hole. Specifically, when the porous body has one through hole, a film thickness difference is likely to occur in the porous film formed on the inner surface of the through hole, and the porous body has a plurality of through holes. A film thickness difference is likely to occur between the porous films formed on the inner surface of each through hole.

  The present invention has been made in view of the above situation, and provides a liquid mixture supply jig capable of uniformly supplying a liquid mixture to a porous body, and a method of manufacturing a separation membrane structure using the same. With the goal.

  A liquid mixture supply jig according to the present invention is a liquid mixture supply jig for supplying a liquid mixture to a porous body having one or more through-holes, and includes a plurality of pieces communicated from a first surface to a second surface. A jig body having a flow path is provided.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the separation membrane structure using the liquid mixture supply jig | tool which can supply a liquid mixture uniformly to a porous body, and it can be provided.

Perspective view of separation membrane structure AA sectional view of FIG. A perspective view of the liquid mixture supply jig as seen from above The perspective view which looked at the liquid mixture supply jig from the lower part A plan view of the liquid mixture supply jig viewed from the second surface side Sectional drawing for demonstrating the manufacturing method of a separation membrane structure Sectional drawing for demonstrating the manufacturing method of a separation membrane structure Sectional drawing for demonstrating the manufacturing method of a separation membrane structure

  Embodiments of the present invention will be described below with reference to the drawings. In the following description of the drawings, the same or similar parts are denoted by the same or similar reference numerals. However, the drawings are schematic, and the ratio of each dimension may be different from the actual one.

(Configuration of separation membrane structure 10)
FIG. 1 is a perspective view of the separation membrane structure 10. FIG. 2 is a cross-sectional view taken along the line AA of FIG. The separation membrane structure 10 includes a support 20, a first seal portion 21, a second seal portion 22, and a separation membrane 23.

  The support 20 is formed in a monolith shape having a plurality of filtration cells CL for circulating a mixed fluid (mixed liquid or mixed gas) to be filtered. The “monolith shape” means a shape having a plurality of communication holes formed in the longitudinal direction, and is a concept including a honeycomb shape. However, the outer shape of the support 20 is not limited to a monolithic shape, and may have one or more filtration cells CL.

  Although the length in particular of the support body 20 is not restrict | limited, For example, it can be 150 mm-2000 mm. Although the diameter in particular of the support body 20 is not restrict | limited, For example, it can be set as 30 mm-220 mm.

  The support 20 has a first end surface S1, a second end surface S2, and a side surface S3. The first end surface S1 is provided opposite to the second end surface S2. The side surface S3 is continuous with the first end surface S1 and the second end surface S2. Each filtration cell CL penetrates the support 20 from the first end surface S1 to the second end surface S2. Each filtration cell CL extends in the longitudinal direction of the support 20. In the present embodiment, the cross section of each filtration cell CL is circular, but is not limited to a circular shape, and may be a polygon more than a triangle.

  In this embodiment, the support body 20 has the base material 20a, the intermediate | middle layer 20b, and the surface layer 20c, as shown in FIG.

  The base material 20a is made of a porous material. As the porous material, for example, a ceramic sintered body, metal, organic polymer, glass, or carbon can be used. Examples of the ceramic sintered body include alumina, silica, mullite, zirconia, titania, yttria, silicon nitride, and silicon carbide. Examples of the metal include aluminum, iron, bronze, silver, and stainless steel. Examples of the organic polymer include polyethylene, polypropylene, polytetrafluoroethylene, polysulfone, and polyimide.

  The base material 20a may contain an inorganic binder. As the inorganic binder, at least one of titania, mullite, easily sinterable alumina, silica, glass frit, clay mineral, and easily sinterable cordierite can be used.

  The average pore diameter of the base material 20a can be set to, for example, 5 μm to 25 μm. The average pore diameter of the substrate 20a can be measured with a mercury porosimeter. The porosity of the base material 20a can be set to 25% to 50%, for example. The average particle diameter of the porous material constituting the substrate 20a can be set to 5 μm to 100 μm, for example. In the present embodiment, the “average particle diameter” is a value obtained by arithmetically averaging the maximum diameters of 30 measurement target particles measured by cross-sectional microstructure observation using SEM (Scanning Electron Microscope).

  The intermediate layer 20b is formed on the base material 20a. The intermediate layer 20b can be composed of the porous material that can be used for the base material 20a. The average pore diameter of the intermediate layer 20b may be smaller than the average pore diameter of the substrate 20a, and may be, for example, 0.005 μm to 5 μm. The average pore diameter of the intermediate layer 20b can be measured with a palm porometer. The porosity of the intermediate layer 20b can be set to, for example, 20% to 60%. The thickness of the intermediate layer 20b can be, for example, 30 μm to 300 μm.

  The surface layer 20c is formed on the intermediate layer 20b. The surface layer 20c can be comprised with the said porous material which can be used for the base material 20a. The average pore diameter of the surface layer 20c may be smaller than the average pore diameter of the intermediate layer 20b, and may be, for example, 0.001 μm to 2 μm. The average pore diameter of the surface layer 20c can be measured with a palm porometer. The porosity of the surface layer 20c can be set to, for example, 20% to 60%. The thickness of the surface layer 20c can be set to 1 μm to 50 μm, for example.

  The first seal portion 21 covers substantially the entire first end surface S1 and part of the side surface S3. The first seal portion 21 suppresses the mixed fluid from infiltrating the first end surface S <b> 1 of the support 20. As a material constituting the first seal portion 21, glass, metal, resin, or the like can be used, and glass is suitable in consideration of consistency with the thermal expansion coefficient of the support 20.

  The second seal portion 22 covers substantially the entire second end surface S2 and a part of the side surface S3. The second seal portion 22 suppresses the mixed fluid from infiltrating the second end surface S <b> 2 of the support 20. As a material constituting the second seal portion 22, glass, metal, resin, or the like can be used, and glass is preferable in consideration of consistency with the thermal expansion coefficient of the support 20.

  The separation membrane 23 is formed on the inner surface of each filtration cell CL formed on the support 20. The separation membrane 23 is formed in a cylindrical shape.

  As a material constituting the separation membrane 23, an inorganic material, a metal, or the like can be used. Examples of the inorganic material for the separation membrane 23 include zeolite, carbon, and silica. The crystal structure of the zeolite constituting the separation membrane 23 is not particularly limited, and for example, LTA, MFI, MOR, FER, FAU, DDR, CHA, BEA and the like can be used. When the separation membrane 23 is a DDR type zeolite membrane, it can be suitably used as a gas separation membrane for selectively separating carbon dioxide. Examples of the metal material of the separation membrane 23 include palladium.

  The thickness of the separation membrane 23 can be arbitrarily set depending on the material type constituting the separation membrane 23, but is preferably 10 μm or less in consideration of the permeation amount of the permeable component that permeates the separation membrane 23 in the mixed fluid. The following is more preferable.

(Liquid mixture supply jig 30)
Next, the configuration of the liquid mixture supply jig 30 used for manufacturing the separation membrane structure 10 will be described. FIG. 3 is a perspective view of the liquid mixture supply jig 30 as viewed from above. FIG. 4 is a perspective view of the liquid mixture supply jig 30 as viewed from below.

  The liquid mixture supply jig 30 includes a jig body 31, a mesh body 32, and a plurality of hair pieces 33.

  The jig body 31 is formed in a cylindrical shape. The outer shape of the jig body 31 is not limited to a cylindrical shape as long as it matches the outer shape of the separation membrane structure 10. The jig body 31 has a first surface T1, a second surface T2, a third surface T3, and a plurality of flow paths FC. The first surface T1 is provided opposite to the second surface T2. The third surface T3 is continuous with the first surface T1 and the second surface T2. Each flow path FC communicates from the first surface T1 to the second surface T2. The position of each flow path FC is not particularly limited, but is preferably evenly distributed as a whole, and particularly preferably coincident with the position of each filtration cell CL of the support 20. The inner diameter of each flow path FC is not particularly limited, but is preferably equal to or larger than the inner diameter of each filtration cell CL.

  The net-like body 32 is disposed on the second surface T2 side of the jig body 31. In the present embodiment, the mesh body 32 is fixed to the second surface T <b> 2 of the jig body 31. The outer edge of the net-like body 32 can be attached to the second surface T2 with an adhesive, for example. The net body 32 only needs to be formed in a net shape, and the shape and size of the net are not particularly limited. The shape and size of the net-like body 32 are preferably matched to the planar shape of the second surface T2. The net-like body 32 can be made of a resin such as PP (polypropylene) or nylon.

  Each hair piece 33 is disposed on the second surface T2 side of the jig body 31. Each hair piece 33 is fixed to the mesh body 32. Each hair piece 33 can be affixed to the mesh body 32 by, for example, an adhesive. Each hair piece 33 should just be formed in hair shape, The shape, length, and thickness are not restrict | limited in particular. Each hair piece 33 may be formed in a straight line shape or may be formed in a wavy line shape. Furthermore, the tip shape of the hair piece can be spherical, needle-like, flat or the like. The length of each hair piece 33 can be 0.5 mm or more and 10 mm or less, for example. The thickness of each hair piece 33 can be, for example, 0.01 mm or more and 1 mm or less.

  In the present embodiment, a plurality of hair bundles 34 are formed by a part of the plurality of hair pieces 33. Each hair bundle 34 is formed in a columnar shape as a whole. Each bristle bundle 34 is arranged outside the outlet of each flow path FC formed on the second surface T2 of the jig body 31. That is, each hair bundle 34 is disposed so as to protrude outward from the outlet of each flow path FC. The number of hair pieces 33 included in each hair bundle 34 is not particularly limited, but may be, for example, 1 or more and 1000 or less. Considering that the liquid mixture flowing out from each flow channel FC is effectively dispersed, for example, when the thickness of the hair piece 33 is 0.1 mm and the inner diameter of the through hole is 2 mm, the hair pieces included in each hair bundle 34 33 is preferably 100 or more. Considering that the liquid mixture flows out smoothly from each flow path FC, it is preferable that the number of hair pieces 33 included in each hair bundle 34 is 300 or less. However, the thickness and number of the hair pieces 33 can be appropriately changed depending on properties such as the viscosity of the liquid mixture.

  Here, FIG. 5 is a plan view of the outlet of the flow path FC formed on the second surface T2 of the jig body 31. FIG. As shown in FIG. 5, the hair bundle 34 is disposed inside the outlet of the flow path FC in a plan view. The hair bundle 34 is arranged in the same shape (that is, circular) as the outlet of the flow path FC in plan view. The plurality of hair pieces 33 included in the hair bundle 34 are scattered inside the outlet of the flow path FC in a plan view. The plurality of hair pieces 33 are preferably arranged evenly on the inside of the outlet of the flow path FC in plan view.

  Here, the occupied area ratio of the hair bundle 34 (the plurality of hair pieces 33) in the total area of the outlet of the flow path FC can be 0.5% or more and 10% or less. By setting the occupation area ratio of the hair bundle 34 in the total area of the outlet of the channel FC to 0.5% or more, the liquid mixture flowing out from the channel FC can be effectively dispersed. By setting the occupied area ratio of the hair bundle 34 in the total area of the outlet of the flow channel FC to 10% or less, the liquid mixture can be smoothly flowed out from the flow channel FC.

(Method for producing separation membrane structure)
A method for manufacturing the separation membrane structure 10 will be described. 6 to 8 are cross-sectional views for explaining a method for manufacturing the separation membrane structure 10.

(1) Formation of Support 20 First, a molded body of the base 20a is formed by molding the raw material of the base 20a into a desired shape using an extrusion molding method, a press molding method, a casting molding method, or the like. Next, the molded body of the base material 20a is fired (for example, 900 ° C. to 1450 ° C.) to form the base material 20a. In the present embodiment, the base material 20a is an example of a “porous body”. As shown in FIG. 6, the base material 20a according to the present embodiment has a plurality of through holes TH for forming a plurality of filtration cells CL.

  Next, as shown in FIG. 6, the upper end portion of the base material 20 a is fixed to the lower end portion of the funnel 40. The funnel 40 has a funnel body 41 and a butterfly valve 42. The funnel body 41 has a storage part 41a and a flow part 41b. The butterfly valve 42 is disposed inside the funnel body 41. The butterfly valve 42 is disposed between the storage part 41a and the flow lower part 41b of the funnel body 41. The butterfly valve 42 can be opened and closed about a shaft 42a. Below the butterfly valve 42, the liquid mixture supply jig 30 described above is disposed. The liquid mixture supply jig 30 is fixed in the flow lower part 41 b of the funnel body 41. In this embodiment, each flow path FC of the liquid mixture supply jig 30 is positioned vertically above each filtration cell CL of the substrate 20a.

  Next, an intermediate layer slurry is prepared using a ceramic raw material having a desired particle diameter, and the intermediate layer slurry is stored in the storage portion 41a of the funnel body 41 as shown in FIG. At this time, the butterfly valve 42 is closed. In the present embodiment, the intermediate layer slurry is an example of a “liquid mixture”.

  Next, the intermediate layer slurry is caused to flow by opening the butterfly valve 42. As shown in FIG. 7, when the butterfly valve 42 starts to open, the intermediate layer slurry flows non-uniformly along the inner wall of the flow lower portion 41 b, but is temporarily blocked by the liquid mixture supply jig 30. It is stored in. As shown in FIG. 8, the intermediate layer slurry temporarily stored on the liquid mixture supply jig 30 flows out uniformly from the respective channels FC of the liquid mixture supply jig 30. The intermediate layer slurry flowing out from each flow channel FC is further rectified more evenly by the hair bundle 34 disposed below each flow channel FC. The hair bundle 34 is preferably close to the inlet of the filtration cell CL. Thereby, the liquid mixture can be smoothly poured from the flow path FC into the filtration cell CL.

  And as above-mentioned, since each flow path FC of the liquid mixture supply jig | tool 30 is located in the vertically upper direction of each filtration cell CL of the base material 20a, the slurry for intermediate | middle layers rectified by the hair | bristle bundle 34 is a base. It flows evenly into each filtration cell CL of the material 20a and flows down inside each filtration cell CL. As a result, a formed body of the intermediate layer 20b is formed on the inner surface of the substrate 20a.

  Next, the molded body of the intermediate layer 20b is fired (for example, 900 ° C. to 1450 ° C.) to form the intermediate layer 20b. As described above, the molded body of the intermediate layer 20b is formed by uniformly flowing the slurry for the intermediate layer from each flow path FC of the liquid mixture supply jig 30, and thus the film thickness between the intermediate layers 20b. The difference is suppressed. In the present embodiment, the intermediate layer 20b is an example of a “porous membrane”.

  Next, a surface layer slurry is prepared using a ceramic raw material having a desired particle diameter, and is stored in the storage portion 41a of the funnel body 41 in the same manner as the intermediate layer slurry (see FIG. 6). Then, the surface layer slurry is caused to flow down by opening the butterfly valve 42. Similar to the intermediate layer slurry (see FIGS. 7 and 8), the surface layer slurry is temporarily stored on the liquid mixture supply jig 30 and then uniformly flows into each filtration cell CL from each channel FC. Thereby, a molded body of the surface layer 20c is formed on the inner surface of the intermediate layer 20b.

  Next, the molded body of the surface layer 20c is fired (for example, 900 ° C. to 1450 ° C.) to form the surface layer 20c. As described above, the molded body of the surface layer 20c is formed by uniformly flowing the surface layer slurry from the respective flow paths FC of the liquid mixture supply jig 30, so that the difference in film thickness between the surface layers 20c is suppressed. It has been. Thus, the support 20 is completed. In the present embodiment, the base material 20a on which the intermediate layer 20b is formed is an example of a “porous body”, and the surface layer 20c is an example of a “porous film”.

(2) Formation of separation membrane 23 The separation membrane 23 is formed on the inner surface of the surface layer 20c. The separation membrane 23 can be formed by a conventionally known method according to the type of membrane. Hereinafter, a method for forming each of the zeolite membrane, the silica membrane, and the carbon membrane will be sequentially described as an example of a method for forming the separation membrane 23. In the present embodiment, the base material 20a (that is, the support 20) on which the intermediate layer 20b and the surface layer 20c are formed is an example of a “porous body”, and the separation membrane 23 is an example of a “porous membrane”. is there.

-Zeolite membrane First, the seed crystal solution containing a zeolite seed crystal is apply | coated to the inner surface of the surface layer 20c. Under the present circumstances, it is preferable to apply | coat a seed crystal solution to the inner surface of the surface layer 20c by the flow-down method similarly to the slurry for intermediate | middle layers mentioned above (refer FIGS. 6-8). Thereby, the zeolite seed crystals can be evenly applied to the inner surface of the surface layer 20c.

  Next, the support 20 is immersed in a pressure resistant container containing a raw material solution in which at least one of a nitrogen adsorbing metal cation and a nitrogen adsorbing metal complex is added to a silica source, an alumina source, an organic template, an alkali source, and water.

  Next, a pressure-resistant container is put into a dryer, and a zeolite membrane is formed by performing heat treatment (hydrothermal synthesis) at 100 to 200 ° C. for about 1 to 240 hours. Next, the support 20 on which the zeolite membrane is formed is washed and dried at 80 to 100 ° C.

  Next, when the organic template is contained in the raw material solution, the support 20 is placed in an electric furnace and heated at 400 to 800 ° C. in the atmosphere for about 1 to 200 hours to burn and remove the organic template. Since the zeolite membrane thus formed is synthesized using the uniformly applied zeolite seed crystals as nuclei, the difference in film thickness between the zeolite membranes is suppressed.

Silica film First, tetraethoxysilane is hydrolyzed in the presence of nitric acid to form a sol solution, and a precursor solution (silica sol solution) is prepared by diluting with ethanol or water.

  Next, the precursor solution is brought into contact with the inner surface of the surface layer 20c. At this time, it is preferable that the precursor solution is brought into contact with the inner surface of the surface layer 20c by a flow-down method, as in the above-described slurry for the intermediate layer (see FIGS. 6 to 8). Thus, the precursor solution can be evenly applied to the inner surface of the surface layer 20c.

  Next, the temperature is raised to 400 to 700 ° C. at 100 ° C./hr and held for 1 hour, and then the temperature is lowered at 100 ° C./hr. A silica film is formed by repeating the above steps 1 to 5 times. Since the silica film formed in this way is formed from the uniformly applied precursor solution, the difference in film thickness between the silica films is suppressed.

-Carbon film First, a thermosetting resin such as an epoxy resin or a polyimide resin, a thermoplastic resin such as polyethylene, a cellulosic resin, or a precursor material thereof, at least one of a nitrogen adsorbing metal cation and a nitrogen adsorbing metal complex A precursor solution is prepared by dissolving in an organic solvent such as methanol, acetone, tetrahydrofuran, NMP, toluene, or water to which is added.

  Next, the precursor solution is brought into contact with the inner surface of the surface layer 20c. At this time, it is preferable that the precursor solution is brought into contact with the inner surface of the surface layer 20c by a flow-down method, as in the above-described slurry for the intermediate layer (see FIGS. 6 to 8). Thus, the precursor solution can be evenly applied to the inner surface of the surface layer 20c.

  Next, a carbon film is formed by performing a heat treatment (for example, 500 ° C. to 1000 ° C.) according to the type of resin contained in the precursor solution. Since the carbon film formed in this way is formed from the uniformly applied precursor solution, the difference in film thickness between the carbon films is suppressed.

(Other embodiments)
As mentioned above, although one Embodiment of this invention was described, this invention is not limited to the said embodiment, A various change is possible in the range which does not deviate from the summary of invention.

  In the above embodiment, the liquid mixture supply jig 30 includes the jig main body 31 and the plurality of hair pieces 33, but may not include the plurality of hair pieces 33. In this case, the mesh body 32 for supporting the plurality of hair pieces 33 is also unnecessary.

  In the above embodiment, the plurality of hair pieces 33 are fixed to the mesh body 32, but may be directly fixed to the second surface T <b> 2 of the jig body 31. In this case, the hair pieces 33 cannot be arranged outside the respective flow paths FC of the support 20, but the liquid mixture traveling from the respective flow paths FC along the second surface T <b> 2 can be smoothly flowed down by the respective hair pieces 33. it can.

  In the said embodiment, although the several hair piece 33 decided to form the several hair | bristle bundle 34, you may arrange | position uniformly on the whole surface of 2nd surface T2.

  In the said embodiment, although the support body 20 decided to have the base material 20a, the intermediate | middle layer 20b, and the surface layer 20c, it does not need to have at least one of the intermediate | middle layer 20b and the surface layer 20c.

  In the above embodiment, the separation membrane structure 10 includes the separation membrane 23 laminated on the support 20, but the separation membrane 23 may not be provided. Further, the separation membrane structure 10 may include another functional film or protective film stacked on the separation film 23. As such a functional film or protective film, an inorganic film such as a zeolite film, a carbon film, or a silica film, or an organic film such as a polyimide film or a silicone film can be used.

  In the above embodiment, the liquid mixture supply jig 30 is fixed inside the funnel 40, but may be fixed inside a known supply pipe. Even in this case, the liquid mixture can be evenly flowed down to the porous body by the liquid mixture supply jig 30.

DESCRIPTION OF SYMBOLS 10 Separation membrane structure 20 Support body 20a Base material 20b Intermediate layer 20c Surface layer 23 Separation membrane 30 Liquid mixture supply jig 31 Jig body 32 Net body 33 Hair piece 34 Hair bundle 40 Funnel 41a Reservoir 41b Flowing part 41 Funnel body 42 Butterfly valve

Claims (11)

A liquid mixture supply jig for pouring the liquid mixture into the one or more through holes formed in the porous body by a flow-down method ,
A liquid mixture supply jig comprising a jig body having a plurality of flow paths communicating from a first surface to a second surface. A plurality of hair pieces arranged on the second surface side of the jig body;
The liquid mixture supply jig according to claim 1. The plurality of hair pieces are fixed to a net-like body,
At least some of the plurality of hair pieces are disposed outside the outlets of the plurality of flow paths formed on the second surface.
The liquid mixture supply jig according to claim 2. The plurality of hair pieces are fixed to the second surface,
The liquid mixture supply jig according to claim 2. Disposing a liquid mixture supply jig including a jig body having a plurality of flow paths communicating from the first surface to the second surface above the porous body having one or more through holes;
Forming a porous film on the inner surface of the one or more through holes by pouring the liquid mixture into the one or more through holes of the porous body through the plurality of flow paths of the liquid mixture supply jig And a process of
A method for producing a separation membrane structure comprising: The liquid mixture supply jig further includes a plurality of hair pieces arranged on the second surface side of the jig body.
The method for producing a separation membrane structure according to claim 5. The plurality of hair pieces are fixed to a net-like body,
At least some of the plurality of hair pieces are disposed outside the outlets of the plurality of flow paths formed on the second surface.
The manufacturing method of the separation membrane structure of Claim 6. The plurality of hair pieces are fixed to the second surface,
The manufacturing method of the separation membrane structure of Claim 6. At least some of the plurality of hair pieces are arranged at an inlet of the one or more through holes formed in the porous body.
The manufacturing method of the separation membrane structure in any one of Claims 6 thru | or 8. The porous body has a plurality of through holes,
Each of the plurality of flow paths of the liquid mixture supply jig is located above each of the plurality of through holes of the porous body in the vertical direction.
The manufacturing method of the separation membrane structure in any one of Claims 6 thru | or 9. A liquid mixture supply jig for supplying a liquid mixture to a porous body having one or more through holes,
A jig body having a plurality of flow paths communicating from the first surface to the second surface;
A plurality of hair pieces arranged on the second surface side of the jig body;
A liquid mixture supply jig comprising:

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