WO2013136869A1 - 分離膜の製造方法、分離膜複合体の製造方法、及び分離膜複合体 - Google Patents
分離膜の製造方法、分離膜複合体の製造方法、及び分離膜複合体 Download PDFInfo
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- WO2013136869A1 WO2013136869A1 PCT/JP2013/052366 JP2013052366W WO2013136869A1 WO 2013136869 A1 WO2013136869 A1 WO 2013136869A1 JP 2013052366 W JP2013052366 W JP 2013052366W WO 2013136869 A1 WO2013136869 A1 WO 2013136869A1
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- Prior art keywords
- separation membrane
- cell
- monolith substrate
- suction
- precursor
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- 238000000926 separation method Methods 0.000 title claims abstract description 388
- 238000000034 method Methods 0.000 title claims abstract description 117
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- 239000007788 liquid Substances 0.000 description 15
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
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- 229910021536 Zeolite Inorganic materials 0.000 description 4
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- 238000001816 cooling Methods 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
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- 230000002950 deficient Effects 0.000 description 2
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 2
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 2
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- 229910052753 mercury Inorganic materials 0.000 description 2
- 229910052863 mullite Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000009719 polyimide resin Substances 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
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- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/021—Carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
- B01D61/362—Pervaporation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
- B01D63/06—Tubular membrane modules
- B01D63/066—Tubular membrane modules with a porous block having membrane coated passages
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0067—Inorganic membrane manufacture by carbonisation or pyrolysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/40—Details relating to membrane preparation in-situ membrane formation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/46—Impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/04—Characteristic thickness
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/28—Degradation or stability over time
Definitions
- the present invention relates to a method for producing a separation membrane, a method for producing a separation membrane complex, and a separation membrane complex. More specifically, a method for producing a separation membrane, a method for producing a separation membrane complex, and a method for producing the separation membrane capable of effectively suppressing the occurrence of a thick film portion in which the thickness of the separation membrane partially increases. It is related with the separation membrane composite provided with the separation membrane obtained by (1).
- a method using selective permeability of a zeolite membrane is known as a method for recovering ethanol produced by such biomass technology. This is to separate ethanol and water by bringing a liquid mixture containing water and ethanol obtained from woody biomass into contact with the zeolite membrane and selectively allowing only water to permeate.
- Carbon membranes have superior acid resistance compared to zeolite membranes, and exhibit stable separation performance over a long period even in the presence of organic acids.
- a typical usage form of the carbon film used for such a purpose one in which the carbon film is disposed on the surface of a cell formed on a porous monolith substrate is known.
- the separation membrane precursor is formed on the surface of the cell by passing the precursor solution of the separation membrane through a plurality of cells formed on the porous monolith substrate.
- the separation membrane precursor include a polyamic acid membrane.
- the monolith substrate is placed in a dryer, and the separation membrane precursor is dried. Thereafter, the dried separation membrane precursor is carbonized by pyrolysis under a reducing atmosphere such as a nitrogen atmosphere to form a carbon membrane (see, for example, Patent Document 1).
- the method of passing the separation membrane precursor solution through the plurality of cells may be referred to as a dip film formation method.
- a method for producing a separation membrane a method for producing a separation membrane has been proposed in which the separation membrane precursor is dried by ventilation drying in which hot air is passed through the cell (see, for example, Patent Documents 2 and 3).
- a separation membrane having a desired separation performance is obtained by repeatedly performing a step of forming a separation membrane precursor and a step of drying the separation membrane precursor a plurality of times. Is manufactured.
- the process of forming the separation membrane precursor may be referred to as a “film forming process”.
- the process of drying the separation membrane precursor may be referred to as “drying process”.
- the conventional separation membrane manufacturing method has a problem that the thickness of the obtained separation membrane may be partially increased.
- the precursor solution is formed on the one end side of the monolith substrate, and the resulting separation membrane has a partial thickness.
- the problem of becoming thicker occurs very frequently.
- the part where the thickness of the separation membrane partially increases may be referred to as a thick film part. If such a thick film portion exists in the separation membrane, cracks are likely to be generated from the thick film portion.
- the separation membrane is disposed on the surface of the cell of the monolith substrate, the separation membrane is easily peeled off from the thick film portion.
- the present invention has been made in view of the above-described problems, and a method for manufacturing a separation membrane capable of effectively suppressing the occurrence of a thick film portion in which the thickness of the separation membrane partially increases, and the separation membrane A method for producing a composite is provided.
- the present invention also provides a separation membrane complex provided with a separation membrane obtained by such a method for producing a separation membrane.
- the following method for producing a separation membrane a method for producing a separation membrane complex, and a separation membrane complex are provided.
- the separation membrane By passing the precursor solution of the separation membrane through the cells of the cylindrical porous monolith substrate in which a plurality of cells are formed so as to extend from the first end surface to the second end surface, From the membrane forming step of forming a separation membrane precursor made of the precursor solution on the surface of the cell, and the opening of the cell in the first end surface or the second end surface of the monolith substrate, the separation membrane A cell suction step of sucking the inside of the cell formed with the precursor, and a drying step of drying the separation membrane precursor formed on the surface of the cell of the monolith substrate sucked in the cell. A method for producing a separation membrane.
- the cell suction step the cell extending direction of the monolith substrate is vertical so that the opening of the cell on the first end surface of the monolith substrate opens downward in the vertical direction.
- the monolith substrate is arranged so that the cell extending direction is vertical, and the state is held for 60 minutes or less, and then the first end surface of the monolith substrate.
- the ratio of the mass of the precursor solution sucked from the cell in the cell suction step to the mass of the precursor solution adhered in the cell is 0.5 to The method for producing a separation membrane according to any one of [1] to [3], which is 2.5%.
- a method for producing a separation membrane complex comprising producing a separation membrane by the method for producing a separation membrane as described, and producing a separation membrane complex comprising the monolith substrate and the separation membrane.
- a cylindrical porous monolith substrate in which a plurality of cells are formed so as to extend from the first end surface to the second end surface, and a separation membrane disposed on the surface of the cell,
- a separation membrane composite in which a ratio of the number of cells not having a thick film portion having a thickness of 5 ⁇ m or more is 80% or more with respect to the number of all the cells.
- the method for producing a separation membrane and the method for producing a separation membrane composite of the present invention it is possible to effectively suppress the generation of a thick membrane part in which the thickness of the separation membrane partially increases. That is, in the method for producing a separation membrane of the present invention, after the membrane formation step, the inside of the cell in which the separation membrane precursor is formed from the opening portion of the cell on the first end surface or the second end surface of the monolith substrate. A cell suction step for suction is provided. By this cell suction step, an excessive precursor solution partially applied to the surface of the cell can be sucked to obtain a separation membrane precursor having a uniform film thickness. Thereby, generation
- the separation membrane composite of the present invention has a cylindrical porous monolith substrate in which a plurality of cells are formed so as to extend from the first end surface to the second end surface, and a cell surface of the monolith substrate.
- a separation membrane Provided with a separation membrane.
- the ratio of the number of cells having no thick film portion having a separation membrane thickness of 5 ⁇ m or more is 80% or more with respect to the total number of cells.
- the separation membrane is difficult to peel off from the surface of the cell, and breakage such as cracks is unlikely to occur in the separation membrane.
- the separation membrane is not easily peeled off and cracks such as those described above, the separation performance of the separation membrane is hardly lowered, and good separation performance can be maintained.
- One embodiment of the method for producing a separation membrane of the present invention is a method for producing a separation membrane comprising a membrane forming step, a cell suction step, and a drying step.
- the manufacturing method of the separation membrane of this embodiment is a manufacturing method of the separation membrane which forms a separation membrane on the surface of the cell 2 of the monolith substrate 1 as shown in FIG.
- FIG. 1 is a perspective view schematically showing a monolith substrate used in one embodiment of the method for producing a separation membrane of the present invention.
- the membrane formation process in the method for manufacturing a separation membrane according to the present embodiment is performed by passing the precursor solution of the separation membrane through the porous monolith substrate cell, so that the precursor solution is applied to the surface of the monolith substrate cell. This is a step of forming a separation membrane precursor.
- the monolith substrate has a cylindrical shape in which a plurality of cells are formed so as to extend from the first end surface to the second end surface.
- the first end surface and the second end surface of the monolith substrate may be collectively referred to simply as “end surface”.
- the cell suction step is a step of sucking the inside of the cell formed with the separation membrane precursor from the opening of the cell on the first end surface or the second end surface of the monolith substrate.
- the drying step is a step of drying the separation membrane precursor formed on the surface of the cell of the monolith substrate sucked in the cell. Since the separation membrane precursor having a uniform film thickness has been obtained by the cell suction process described above, by performing such a drying process, generation of a thick film portion where the thickness of the separation film is partially increased is generated. It can be effectively suppressed. In the separation membrane manufacturing method of the present embodiment, it is preferable that the drying step drys the separation membrane precursor by performing ventilation drying in which hot air is passed through the cell.
- the above-described film forming process, cell suction process and drying process may be set as a set of processes, and this set of processes may be repeated two or more times.
- the separation membrane precursor made of the precursor solution is formed on the surface of the cell by passing the precursor solution of the separation membrane through the cell of the porous monolith substrate.
- the inside of the cell in which the separation membrane precursor is formed is sucked from the opening of the cell on the first end surface or the second end surface of the monolith substrate.
- the separation membrane precursor formed on the surface of the monolith substrate cell sucked in the cell is dried.
- the series of steps up to here is a set of steps described above.
- a separation membrane precursor made of a precursor solution is further formed on the surface of the cell.
- the precursor solution is applied to the surface of the dried separation membrane precursor, and two layers of the separation membrane precursor are laminated.
- the separation membrane precursor laminated in two layers is dried again.
- FIG. 2 is an explanatory view schematically showing an example of a membrane forming step in one embodiment of the method for manufacturing a separation membrane of the present invention.
- the monolith substrate 1 is accommodated in a tubular film forming container 32 having both ends opened in the longitudinal direction, and the precursor solution 31 is placed in the cell 2 from the second end face 12 side of the monolith substrate 1.
- the film forming container 32 is formed using an annular sealing material 33 such as packing on the first end surface 11 and the second end surface 12 of the monolith substrate 1. It is preferable to fix hermetically inside.
- Such a film forming process may be referred to as a film forming process using a dip film forming method.
- the film forming step in the separation membrane manufacturing method of the present embodiment is not limited to the film forming step using the dip film forming method as shown in FIG. That is, if the precursor solution is applied to the surface side of the cell and a separation membrane precursor composed of the precursor solution can be formed, the membrane forming step in the conventionally known separation membrane manufacturing method is performed. It can be used suitably. For example, as another film forming process, a film forming process using a pouring method or the like can be cited.
- the precursor solution is transferred from the second end surface of the monolith substrate at a speed of about 0.3 to 300 cm / min. More preferably, it is fed into each cell of the substrate.
- the monolith substrate is arranged such that the second end surface 12 of the monolith substrate 1 is above the first end surface 11. It is preferable to carry out in a state where the material 1 is disposed in the film forming container 32.
- This film forming step is more preferably performed in a state where the angle formed between the extending direction of the cells 2 of the monolith substrate 1 and the vertical direction is in the range of ⁇ 10 ° to 10 °. Furthermore, in the film forming process, it is more preferable that the angle formed by the extending direction of the cell 2 of the monolith substrate 1 and the vertical direction is closer to 0 °.
- FIG. 3 is a perspective view schematically showing a monolith substrate obtained by forming a membrane and having a separation membrane precursor formed thereon.
- the separation membrane precursor solution used in the membrane formation process it is most preferable to use a polyamic acid solution that has been widely used in the production of separation membranes (eg, carbon membranes).
- the polyamic acid solution is obtained by dissolving polyamic acid, which is a precursor of a polyimide resin, in an appropriate organic solvent such as N-methyl-2-pyrrolidone (NMP) or N, N-dimethylacetamide (DMAc).
- NMP N-methyl-2-pyrrolidone
- DMAc N, N-dimethylacetamide
- concentration of the polyamic acid in the polyamic acid solution is not particularly limited, but is preferably 1 to 20% by mass from the viewpoint of making the solution easy to form a film.
- the concentration of the polyamic acid in the polyamic acid solution is more preferably 3 to 15% by mass, and particularly preferably 5 to 10% by mass.
- the “monolith substrate” in the present invention is a columnar substrate having a first end surface and a second end surface, and a plurality of cells extending from the first end surface serving as a fluid flow path to the second end surface are formed. It means a lotus root or honeycomb substrate.
- Preferred examples of the material of the monolith substrate include ceramic materials such as alumina, silica, cordierite, mullite, titania, zirconia, and silicon carbide from the viewpoint of strength and chemical stability.
- the porosity of the monolith substrate is preferably 25 to 55% from the viewpoint of the strength and permeability of the porous substrate.
- the average pore diameter of the porous substrate is preferably 0.005 to 5 ⁇ m. The porosity and average pore diameter of the porous substrate are values measured with a mercury porosimeter.
- the shape of the monolith substrate for example, the shape of the cross section perpendicular to the cell extending direction is preferably a circular, elliptical, or polygonal cylindrical shape.
- the overall outer diameter of the monolith substrate is preferably 10 to 300 mm, more preferably 20 to 250 mm, and particularly preferably 30 to 200 mm. If the overall outer diameter of the monolith substrate is less than 10 mm, the number of cells that can be formed on the monolith substrate may be reduced. Moreover, when the whole outer diameter of a monolith base material exceeds 300 mm, a monolith base material will become large too much, and manufacture of a separation membrane may become difficult.
- the overall outer diameter of the monolith substrate means the diameter of the cross section (ie, circle) when the shape of the cross section perpendicular to the cell extending direction of the monolith substrate is a circle.
- the “outer diameter of the monolith substrate” means the diameter of a circle having the same cross-sectional area as that of the cross section when the shape of the cross section perpendicular to the cell extending direction of the monolith substrate is not a circle. Means.
- the length of the monolith substrate in the cell extending direction is preferably 30 to 2000 mm, more preferably 100 to 1700 mm, and particularly preferably 150 to 1500 mm.
- the membrane area of the separation membrane may be small.
- the number of cells formed on the monolith substrate is preferably 1 to 10,000, preferably 10 to 5000, and 30 to 2500. It is preferable that When the number of cells exceeds 10,000, it may be difficult to manufacture and handle the monolith substrate.
- the film forming step it is preferable to perform film formation after at least a part of the outer peripheral surface of the monolith substrate is sealed using a seal tape or the like.
- a seal tape or the like By comprising in this way, when passing a precursor solution in a cell, it can prevent that a precursor solution adheres other than the surface of a cell.
- the entire monolith substrate or the surface of the cell on which the separation membrane precursor is formed may be preheated to 50 to 350 ° C. before film formation.
- preheating is performed, drying in the drying process can be accelerated, and separation performance of the finally obtained separation membrane can be improved.
- (1-2) Cell suction step In the separation membrane manufacturing method of the present embodiment, after the film forming step, the inside of the cell in which the separation membrane precursor is formed from the opening of the cell on the first end surface or the second end surface of the monolith substrate. A cell suction step for suction is performed. By providing such a cell suction step, an excessive precursor solution partially applied to the surface of the cell can be sucked to obtain a separation membrane precursor having a uniform film thickness. Thereby, generation
- the precursor solution In the film forming process of forming the separation membrane precursor by passing the precursor solution through the cell of the monolith substrate, the precursor solution is excessively left in the cell at the time of film formation, and the film thickness is uniform. It may be difficult to obtain a separation membrane precursor. In particular, the excessive precursor solution remaining excessively in the cell is likely to partially accumulate in a part of the cell. That is, in the conventional separation membrane manufacturing method, the excess precursor solution remaining in the cell excessively increases the thickness of the separation membrane precursor, and even in the obtained separation membrane, In particular, the thick film portion has a thick film.
- the body solution is removed by aspiration. Thereby, the thickness of the precursor solution applied to the surface side of the cell becomes more uniform.
- the thick film part means, for example, a part having a film thickness of 5 ⁇ m or more.
- the method for sucking the inside of the cell is not particularly limited.
- the second end face is opened to the atmosphere, and the second end face is It is preferable that the sucked gas flows in the cell toward one end face.
- the surplus precursor solution is discharged from the cell opening on the first end face of the monolith substrate by riding on this gas flow.
- FIG. 4 is a perspective view schematically showing an example of a cell suction step in one embodiment of the separation membrane manufacturing method of the present invention.
- the monolith substrate 1 when the monolith substrate 1 is arranged so that the opening of the cell 2 in the first end surface 11 opens downward in the vertical direction, the cell 2 in the first end surface 11. It is more preferable to suck the inside of the cell 2 from the opening.
- the suction removal of the excess precursor solution is performed more efficiently. It can be carried out.
- the thick film portion is more on the end surface side (for example, the first end surface side) vertically below in the film forming process using the dip film forming method described above. Many have been confirmed to occur. For this reason, by sucking the inside of the cell from the end surface side vertically below, it is possible to preferentially suck a portion where a thick film portion may occur more. Thereby, generation
- FIG. 4 an example in which the opening of the cell 2 in the first end face 11 of the monolith substrate 1 is arranged so as to open downward in the vertical direction is shown.
- the opening of the cell 2 in the first end surface 11 of the monolith substrate 1 is directed downward in the vertical direction. It may be arranged to open.
- the monolith substrate 1 is disposed so that the first end surface 11 is on the lower side, and the film forming process is performed.
- the cell suction step may be performed as shown in FIG. 4 while maintaining the state to be the side.
- a hollow tubular member 21 is connected to a suction pump 20 that can be evacuated.
- the suction pump 20 After operating the suction pump 20, the other end of the tubular member 21 is pressed against the first end surface 11 of the monolith substrate 1, and the inside of the cell 2 is opened from the opening portion of the cell 2 opened on the first end surface 11.
- the excess precursor solution can be suctioned and removed more efficiently.
- a hollow tube shape or a hose shape can be used.
- a jig for appropriately adjusting the suction diameter may be attached to the suction end of the tubular member.
- FIG. 5A to FIG. 5C are explanatory diagrams for explaining the step of sequentially sucking the inside of the cell in the cell suction step.
- 5A to 5C show a cross section parallel to the cell extending direction of the monolith substrate.
- 5A to 5C show an example in which the inside of the cell 2 is sequentially sucked in the cell sucking step.
- FIG. Good even if all the cells 2 opened in the first end face 11 are sucked at a time, FIG. Good.
- the amount of the excess precursor solution is different for each cell 2, so that the suction of the cells 2 having a large suction resistance may not be sufficiently performed. is there.
- the amount of the excessive precursor solution is large. Therefore, when the inside of the cell 2 is actively suctioned, as described above, It is more preferable to suck the inside of the cell 2 while moving it.
- the number of cells 2 sucked at a time when the cells 2 are sucked sequentially there is no particular limitation on the number of cells 2 sucked at a time when the cells 2 are sucked sequentially.
- the inside of the cell may be sucked for each cell. Further, for example, the inside of the cell may be sucked every 2 to 20 cells. If the number of cells sucked at one time is too large, a cell having a large suction resistance may not be sufficiently sucked. If the number of cells sucked at one time is too small, the time required for the suction process may become longer, although it depends on the total number of cells formed on the monolith substrate 1.
- the suction time required per 1 cm 2 of the first end face of the monolith substrate is, for example, preferably 0.1 to 3 minutes, more preferably 0.3 to 2 minutes, Particularly preferred is 5 to 1.5 minutes. If the suction time required per 1 cm 2 of the first end face of the monolith substrate is less than 0.1 minute, suction in the cell is not sufficiently performed, and a large amount of excess precursor solution remains in the cell. Sometimes. If it is in the range of the said suction time, the suction removal of the excess precursor solution can be performed favorably.
- the cell suction step is a step for removing the excess precursor solution by suction
- “the mass of the precursor solution sucked from inside the cell in the cell suction step with respect to the mass of the precursor solution adhered in the cell It is also possible to determine the suction state in the cell based on the “ratio”.
- the above-mentioned “mass of the precursor solution attached in the cell” means an actual mass of the precursor solution actually attached in the cell in the film forming process.
- the “mass of the precursor solution adhered in the cell” can be calculated by obtaining a difference between the amount of the precursor solution used in the film forming process and the amount of the precursor solution collected after the film forming process.
- the mass of the precursor solution sucked from the cell in the cell sucking step is obtained by collecting the sucked precursor solution by providing a drain trap or the like on the tubular member that sucks the inside of the cell. It can be determined by measuring the mass of the solution.
- the ratio of the mass of the precursor solution sucked from the cell in the cell suction process to the mass of the precursor solution adhered in the cell in the film forming process is simply referred to as “the mass of the precursor solution sucked. % (%) ”Or“ aspiration amount (%) ”.
- the mass ratio (%) of the sucked precursor solution is preferably 0.1 to 10%, more preferably 0.5 to 5%, and more preferably 1.5 It is particularly preferable that the content be ⁇ 2.5%. If the mass ratio (%) of the sucked precursor solution is less than 0.1%, an excessive precursor solution may still remain in the cell. If the mass ratio (%) of the precursor solution to be sucked exceeds 10%, the precursor solution constituting the normal separation membrane precursor may be discharged out of the cell by suction.
- the amount of intake air per cell is preferably 0.2 to 5 L / min, more preferably 1 to 3 L / min, and 1.5 to 2. Particularly preferred is 5 L / min. If the amount of intake air per cell is less than 0.2 L / min, excess precursor solution tends to remain in the cell. When the amount of intake air per cell exceeds 5 L / min, it becomes easy to create a portion that is partially sucked.
- the monolith substrate 1 is arranged so that the extending direction of the cell 2 is vertical, and the state is maintained for a certain period of time.
- the inside of the cell 2 may be sucked from the opening of the cell 2 in FIG. Specifically, the inside of the cell 2 may be sucked after holding the state in which the monolith substrate 1 is arranged so that the extending direction of the cell 2 is vertical for 60 minutes or less.
- the monolith substrate 1 may be arranged so that the extending direction of the cell 2 is vertical, and the inside of the cell 2 may be sucked immediately after that.
- the suction from the opening of the cell 2 opened in the first end surface 11 can be performed more favorably. That is, the necessary suction time can be shortened by maintaining the state of the monolith substrate 1 described above for a time of 60 minutes or less.
- the monolith substrate 1 it is preferable to hold it in a stable state so that the monolith substrate 1 does not move. If the holding time is too short, the amount of the precursor solution 31 that hangs down due to its own weight is small, so that the effect of shortening the suction time may not be sufficiently obtained.
- the amount of the precursor solution 31 that hangs down by its own weight may hardly increase thereafter.
- the monolith substrate 1 is arranged so that the extending direction of the cell 2 is vertical and the suction in the cell 2 is started immediately thereafter, Since the solution hangs down due to its own weight, the efficiency of suction may be improved.
- (1-3) Drying step In the separation membrane manufacturing method of the present embodiment, after the cell suction step, a drying step of drying the formed separation membrane precursor is performed.
- the drying method in the manufacturing method of a conventionally well-known separation membrane can be used suitably.
- FIG. 6 it is preferable to dry the separation membrane precursor 3 by performing ventilation drying in which hot air 15 is passed through the cells 2 of the monolith substrate 1 on which the separation membrane precursor 3 is formed. .
- ventilation drying in which hot air 15 is passed through the cells 2 of the monolith substrate 1 on which the separation membrane precursor 3 is formed.
- FIG. 6 is explanatory drawing which shows an example of the drying process in one Embodiment of the manufacturing method of the separation membrane of this invention.
- a dryer 14 is disposed on the first end surface 11 side of the monolith substrate 1, and hot air 15 is blown from the dryer 14 toward the first end surface 11 of the monolith substrate 1.
- An example of hot air drying is shown.
- the hot air 15 heated to a predetermined temperature is sent from the opening of the cell 2 opened in the first end surface 11 of the monolith substrate 1.
- circulated the inside of the cell 2 is exhausted from the opening part of the cell 2 opened to the 2nd end surface 12 side of the monolith base material 1.
- FIG. thus, by passing the hot air 15 (ventilated gas) through the cell 2, the separation membrane precursor 3 formed on the surface of the cell 2 is dried.
- the entire separation membrane precursor 3 such as a polyamic acid membrane is uniformly heated by the hot air 15, and drying and imidization proceed uniformly from the surface of the separation membrane precursor 3.
- the temperature of the hot air passing through the cell is preferably 30 to 300 ° C., more preferably 50 to 200 ° C., and further preferably 70 to 190 ° C. If the temperature of the hot air is less than 30 ° C., it may take too much time for the separation membrane precursor to dry. When the temperature of the hot air exceeds 300 ° C., the separation membrane precursor may be burned by drying for a long time.
- the wind speed of the hot air is preferably 0.5 to 30 m / s, more preferably 1 to 15 m / s, and further preferably 5 to 10 m / s.
- the wind speed of hot air is the speed of hot air when passing through the cell. When the wind speed of the hot air is less than 0.5 m / s, drying and imidization of the separation membrane precursor may be uneven. When the wind speed of hot air exceeds 30 m / s, movement of the solution in the separation membrane precursor occurs, and film formation may become non-uniform.
- the separation membrane precursor is dried and imidized.
- the thermal expansion is caused when the separation membrane precursor is imidized. May cause cracks in the monolith substrate.
- imidation mentioned above may not be performed by ventilation drying, but an imidization drying means (imidation furnace) which can control a rate of temperature rise may be used.
- the film thickness of the separation membrane precursor after drying does not reach the desired thickness by one film forming process, cell suction process and drying process, until the desired film thickness is obtained.
- the film forming step, the cell suction step and the drying step may be repeated a plurality of times (for example, 3 to 5 times).
- the separation membrane manufacturing method of the present embodiment may further include a carbonization step of obtaining a separation membrane by pyrolyzing and carbonizing the separation membrane precursor dried in the drying step.
- This carbonization step is a step performed when the separation membrane to be manufactured is a carbon membrane.
- the separation membrane precursor obtained through the film forming step and the drying step is imidized to obtain a polyimide membrane, and the obtained polyimide membrane is heated.
- a separation membrane carbon membrane can be obtained by decomposing and carbonizing.
- the film forming process, the cell suction process, and the drying process are repeatedly performed a plurality of times, the required number of film forming processes, the cell suction process, and the drying process are all completed, and the separation membrane precursor having a desired film thickness is obtained. After being obtained, it is preferable to perform a carbonization step.
- the temperature during the carbonization step is preferably 400 to 1000 ° C.
- a separation membrane can be obtained by pyrolyzing and carbonizing a dried separation membrane precursor (more specifically, a polyimide membrane) in such a temperature range. For example, if carbonization is performed at a temperature of less than 400 ° C., the polyimide membrane is not sufficiently carbonized, and the selectivity and permeation rate as a molecular sieve membrane may be reduced. On the other hand, when carbonization is performed at a temperature exceeding 1000 ° C., the permeation rate decreases due to shrinkage of the pore diameter of the separation membrane.
- the thickness of the finally obtained separation membrane is preferably 0.1 to 10 ⁇ m, more preferably 0.5 to 5 ⁇ m. If the thickness of the separation membrane is less than 0.1 ⁇ m, it may be difficult to obtain sufficient selectivity due to insufficient thickness, and if it exceeds 10 ⁇ m, the thickness may be too thick and the permeation flow rate may be too small. is there.
- a separation membrane produced by the separation membrane production method of the present embodiment can provide high separation performance when used for separation of water and ethanol.
- Such a separation membrane can be suitably used as a separation membrane when recovering ethanol from a liquid mixture containing water and ethanol obtained from biomass.
- a separation membrane constituting the separation membrane composite is produced according to the separation membrane production method of the present invention. That is, the method for producing a separation membrane composite of the present embodiment comprises a step of producing a separation membrane in a porous monolith substrate cell by the method for producing a separation membrane of the present invention described so far. It is a manufacturing method of a membrane composite.
- a separation membrane composite of the present embodiment it is possible to easily manufacture a separation membrane composite including a separation membrane having a small thick film portion where the thickness of the separation membrane is partially increased. it can.
- the separation membrane is difficult to peel off from the surface of the cell, and breakage such as cracks is unlikely to occur in the separation membrane.
- the separation membrane is not easily peeled off and cracks such as those described above, the separation performance of the separation membrane is hardly lowered, and good separation performance can be maintained.
- the step of producing the separation membrane, the selection of the monolith substrate, and the like can be performed according to the method for producing the separation membrane of the present embodiment described so far. it can.
- the separation membrane complex of this embodiment is a separation membrane complex 200 including a porous monolith substrate 101 and a separation membrane 103 as shown in FIGS. 7 and 8.
- the monolith substrate 101 has a cylindrical shape in which a plurality of cells 102 are formed so as to extend from the first end surface 111 to the second end surface 112.
- the separation membrane 103 is disposed on the surface of the cell 102 formed on the monolith substrate 101.
- FIG. 7 is a perspective view schematically showing one embodiment of the separation membrane composite of the present invention.
- FIG. 8 is a cross-sectional view schematically showing a cross section cut in parallel to the cell extending direction of one embodiment of the separation membrane composite of the present invention.
- the ratio of the number of cells 102 a that do not have the thick film portion 105 with the thickness of the separation membrane 103 of 5 ⁇ m or more is 80% or more with respect to the number of all cells 102. It is.
- the separation membrane 103 is disposed on the surface of the plurality of cells 102 formed on the monolith substrate 101 so as to extend from the first end surface 111 to the second end surface 112.
- a portion where the thickness of the separation membrane 103 is 5 ⁇ m or more is referred to as a thick film portion 105.
- a cell 102 having a portion having a thickness of 5 ⁇ m or more is defined as a cell 102b having a thick film portion 105.
- a cell 102 having no portion with a thickness of 5 ⁇ m or more is defined as a cell 102a having no thick film portion 105.
- the cell 102a having no thick film portion 105 means that the thickness of the separation membrane 103 disposed on the surface of the cell 102a is less than 5 ⁇ m.
- the ratio of the number of cells 102 a that do not have such a thick film portion 105 is 80% or more with respect to the number of all cells 102. In other words, the ratio of the number of cells 102b having the thick film portion 105 is less than 20% with respect to the number of all cells 102.
- the separation performance of the separation membrane 103 is deteriorated. That is, when the ratio of the number of cells 102a that do not have the thick film portion 105 is less than 80%, the separation performance of the separation membrane 103 is deteriorated.
- the separation membrane 103 is disposed in close contact with the surface of the cell 102, but if the film thickness portion 105 exists in the separation membrane 103, the separation membrane 103 is easily peeled off from the thick film portion 105. .
- a defect such as a crack may easily occur in the thick film portion 105 where the separation film is locally thick.
- the ratio of the number of cells 102a that do not have the thick film portion 105 is preferably 90% or more, and 95% or more with respect to the number of all cells 102. More preferably it is. In the separation membrane composite 200 of the present embodiment, it is particularly preferable that all the cells 102 are cells 102 a that do not have the thick film portion 105.
- Such a separation membrane composite 200 of the present embodiment can be manufactured by the separation membrane manufacturing method of the present invention described so far. That is, in the conventional manufacturing method, it is impossible to make the ratio of the number of cells 102a not having the thick film portion 105 80% or more.
- the ratio of the number of cells having no thick film portion is 80% or more. The separation membrane composite can be produced satisfactorily.
- the average thickness of the separation membrane 103 disposed on the surface of the cell 102 is preferably 0.1 to 3 ⁇ m, and preferably 0.5 to 3 ⁇ m. More preferably, it is 1 to 3 ⁇ m. If the average thickness of the separation membrane 103 is less than 0.1 ⁇ m, the separation membrane itself may be too thin, and the separation performance of the separation membrane composite 200 may deteriorate. On the other hand, if the average thickness of the separation membrane 103 exceeds 3 ⁇ m, the separation membrane is likely to be cracked or peeled off, and the amount of ethanol leakage may be too large.
- the thickness of the separation membrane can be measured by the following method. First, the monolith substrate on which the separation membrane is formed is split in the cell extending direction. And the cross section of the cell is observed with SEM (scanning electron microscope), and the film thickness of a separation membrane is measured. For all the cells formed on the monolith substrate, the thickness of the portion where the thickness of the separation membrane is maximized is measured. When the maximum part of the thickness of the separation film formed on the surface of each cell is 5 ⁇ m or more, the cell is a cell having a thick film part. On the other hand, when the maximum portion of the thickness of the separation membrane formed on the surface of each cell is less than 5 ⁇ m, the cell is a cell having no thick film portion. By measuring the thickness of the separation membrane, the ratio of the number of cells having no thick film portion can be obtained.
- the average thickness of the separation membrane can be measured by the following method. First, the monolith substrate on which the separation membrane is formed is split in the cell extending direction. And the cross section of the cell is observed with SEM (scanning electron microscope), and the film thickness of a separation membrane is measured. Measurement of the thickness of such a separation membrane is performed at 10 or more locations per cell. The average value of the film thickness measured at each location is calculated. This average value is the “average thickness of the separation membrane”.
- the material of the monolith substrate ceramic materials such as alumina, silica, cordierite, mullite, titania, zirconia, silicon carbide and the like can be given as preferable examples from the viewpoint of strength and chemical stability.
- the porosity of the monolith substrate is preferably 25 to 55% from the viewpoint of the strength and permeability of the porous substrate.
- the average pore diameter of the porous substrate is preferably 0.005 to 5 ⁇ m.
- the porosity and average pore diameter of the porous substrate are values measured with a mercury porosimeter.
- the shape of the monolith substrate for example, the shape of the cross section perpendicular to the cell extending direction is preferably a circular, elliptical, or polygonal cylindrical shape.
- the overall outer diameter of the monolith substrate is preferably 10 to 300 mm, more preferably 20 to 250 mm, and particularly preferably 30 to 200 mm. If the overall outer diameter of the monolith substrate is less than 10 mm, the number of cells that can be formed on the monolith substrate may be reduced. Moreover, when the whole outer diameter of a monolith base material exceeds 300 mm, a monolith base material will become large too much, and manufacture of a separation membrane may become difficult.
- the “outer diameter of the monolith substrate” means the diameter of the cross section (ie, circle) when the shape of the cross section perpendicular to the cell extending direction of the monolith substrate is a circle. Means. In addition, the “outer diameter of the monolith substrate” is the diameter of a circle having the same cross-sectional area as the cross-section when the shape of the cross section perpendicular to the cell extension direction of the monolith substrate is not a circle. Means.
- the length of the monolith substrate in the cell extending direction is preferably 30 to 2000 mm, more preferably 100 to 1700 mm, and particularly preferably 150 to 1500 mm.
- the membrane area of the separation membrane may be small.
- the number of cells formed on the monolith substrate is preferably 1 to 10,000, preferably 10 to 5000, and 30 to 2500. It is preferable that When the number of cells exceeds 10,000, it may be difficult to manufacture and handle the monolith substrate.
- the material of the separation membrane is not particularly limited as long as it can separate at least one component from various mixtures.
- the separation membrane is preferably a carbon membrane.
- a carbon membrane produced using a polyimide solution can be cited as a suitable example.
- Such a carbon membrane can be manufactured by performing the membrane formation process, the cell suction process, the drying process, and the carbonization process described in the embodiment of the separation membrane manufacturing method of the present invention described above. .
- the polyamic acid solution is obtained by dissolving polyamic acid, which is a polyimide resin precursor, in an appropriate organic solvent such as N-methyl-2-pyrrolidone (NMP) or N, N-dimethylacetamide (DMAc).
- concentration of the polyamic acid in the polyamic acid solution is not particularly limited, but is preferably 1 to 20% by mass from the viewpoint of making the solution easy to form a film.
- concentration of the polyamic acid in the polyamic acid solution is more preferably 3 to 15% by mass, and particularly preferably 5 to 10% by mass.
- a porous monolith substrate serving as a substrate for producing a separation membrane was prepared.
- the material of the monolith substrate was alumina.
- the shape of the monolith substrate is a cylindrical shape having a first end face and a second end face. The diameter of the first end face and the second end face is 30 mm, and the length in the cell extending direction is 1000 mm. It was.
- 50 cells extending from the first end surface to the second end surface are formed.
- the shape of the opening of the cell was a circle.
- the diameter of the opening of one cell was 2.5 mm.
- a seal tape was wound around the outer peripheral surface of the monolith substrate to prevent the precursor solution from adhering to the surface other than the surface of the cell of the monolith substrate.
- Such a monolith substrate was placed so that the cell extending direction was the vertical direction, and the precursor solution was fed into each cell using a liquid feed pump (film forming step).
- a polyamic acid solution (U-Vanice-A (trade name) from Ube Industries, Ltd.) having a polyamic acid concentration of 10% by mass using N-methyl-2-pyrrolidone (NMP) as a solvent was used.
- NMP N-methyl-2-pyrrolidone
- the precursor solution was fed for 30 seconds at a speed of 200 cm / min from one opening of each cell.
- a polyamic acid film as a separation membrane precursor was formed in a cell of the monolith substrate.
- the viscosity of the used polyamic acid solution at 25 ° C. was 0.15 Pa ⁇ s.
- the opening of the cell at the first end face of the monolith substrate on which the polyamic acid film was formed was opened downward in the vertical direction, and the monolith substrate was arranged so that the cell extending direction was vertical.
- suction process which removes a part of polyamic-acid solution was performed by attracting
- the suction in the cell was performed by connecting one end of a suction tube having an inner diameter of 6 mm to a suction pump and pressing the other end of the suction tube against the first end surface of the monolith substrate.
- a silicon tube was used as the suction tube.
- the other end of the suction tube When the other end of the suction tube is pressed against the first end surface of the monolith substrate, the other end of the suction tube is moved evenly on the first end surface, and sequentially, the polyamic acid solution is uniformly distributed from all cells. Was removed by suction.
- the suction in the cell was performed for 15 minutes. That is, the other end of the suction tube was moved uniformly on the first end face for 15 minutes to perform suction in the cell.
- the polyamic acid solution excessively applied in the cell was removed by suction to prepare a separation membrane precursor having a predetermined film thickness.
- the suction time per 1 cm 2 of the first end face of the monolith substrate was 2.12 minutes.
- the above “suction time per 1 cm 2 ” means that the cross-sectional area of the monolith substrate is 7.07 cm 2 , the cell opening ratio is 34.7%, and the area of the cell opening is 2.45 cm 2 .
- a suction pump having a suction capacity of 12 L / min was used.
- the ratio of the mass of the polyamic acid solution removed by suction with respect to the mass of the polyamic acid solution adhering in the cell was determined by the following formula (1).
- “the mass of the polyamic acid solution adhering in the cell” is “adhesion amount”
- “the mass of the polyamic acid solution removed by suction” is “the amount removed by suction”.
- the ratio of the mass of the polyamic acid solution removed by suction shown in the following formula (1) is also referred to as “suction amount (%)”.
- Suction amount (%) Amount removed by suction / Amount of adhesion ⁇ 100 (1)
- Table 1 shows the diameter (mm) of the end face of the monolith substrate, the length (mm) in the cell extending direction, the number of cells (pieces), and the cell diameter (mm).
- the diameter (mm) of the end surface of the monolith substrate is the diameter of the first end surface and the second end surface of the monolith substrate.
- the number of cells (pieces) is formed on the monolith substrate. This is the number of cells, and the cell diameter is the diameter of the opening of the cell.
- Table 1 shows the suction time (min) and the suction amount (%) for sucking the inside of the cell.
- the suction amount (%) is the suction amount (%) in the cell suction process performed after the completion of the first film forming process.
- a drying step for drying and imidizing the separation membrane precursor made of the polyamic acid membrane was performed.
- the separation membrane precursor was dried by passing hot air at 150 ° C. from the opening at the first end face of the cell toward the opening at the second end face for 70 minutes.
- the wind speed of the hot air was 10 m / s.
- the cell opening at the first end face of the monolith substrate opens downward in the vertical direction, and the cell extension direction of the monolith substrate is vertical, as in the cell suction step. It carried out in the state arranged to.
- the temperature of the hot air was further increased to 250 ° C., and the hot air was allowed to pass through the inside of the cell for 15 minutes.
- the separation membrane precursor made of the polyamic acid membrane was dried and imidized.
- the above-mentioned film forming process, cell suction process, and drying process were set as a set of processes, and the set of processes was repeated three times, and then the monolith substrate was heat-treated at 800 ° C. in a vacuum box furnace.
- the polyimide membrane obtained by imidization was carbonized, and a separation membrane (carbon membrane) having a thickness of about 1 ⁇ m was obtained.
- the thickness of the obtained separation membrane was measured by the following method, and the “occurrence rate (%) of the thick film portion” was obtained from the measurement result.
- a range of 50 mm from the first end face of the monolith substrate on which the separation membrane was formed was split in the cell extending direction. And the cross section of the cell was observed with SEM (scanning electron microscope), and the film thickness of the separation membrane was measured.
- the 1st end surface of a monolith base material is an end surface used as the downward side of a perpendicular direction in the film forming process of the 1st time, a cell suction process, and a drying process.
- the thicknesses of the portions where the thickness of the separation membrane is maximum were measured in the observed range.
- the percentage of the value obtained by dividing the number of cells having the maximum thickness of the separation membrane of 5 ⁇ m or more by the total number of cells was taken as “thick film portion occurrence rate (%)”.
- Table 1 shows the incidence (%) of the thick film portion of the separation membrane obtained in Example 1.
- FIG. 9 is a schematic view of an osmosis vaporizer used for evaluation of water / ethanol separation performance in Examples.
- the monolith substrate 100 on which the separation membrane is formed is housed in a cylindrical container 55, and a gap between the monolith substrate 100 and the inner peripheral surface of the container 55 is formed between the sealing material 56 at the outer peripheral portions at both ends.
- a supply liquid 59 heated to a predetermined temperature in a beaker 58 accommodated in a thermostatic chamber 57 is circulated to circulation lines 71 to 73 by a circulation pump 60, and the inside of a container 55 disposed in the middle of the circulation lines 71 to 73 is stored.
- the monolith substrate 100 was passed through the cell.
- reference numeral 90 denotes a stirrer for stirring the supply liquid 59
- reference numeral 91 denotes a cooling pipe attached to the upper part of the beaker 58.
- As the supply liquid 59 a water / ethanol mixed liquid having a water / ethanol ratio (mass ratio) of 10/90 was used, and the temperature of the supply liquid was set to 70 ° C. to evaluate the water / ethanol separation performance of the separation membrane.
- an ethanol permeation flow rate (kg / m 2 h) and a water permeation flow rate (kg / m 2 h) were used. Table 1 shows the values of the ethanol permeation flow rate (kg / m 2 h) and the water permeation flow rate (kg / m 2 h).
- Example 2 A separation membrane was produced in the same manner as in Example 1 except that the suction time in the cell suction step was changed as shown in Table 1. About the obtained separation membrane, the incidence (%) of the thick film portion was determined. The obtained separation membrane was subjected to a pervaporation test. The results are shown in Table 1.
- Example 4 A separation membrane was produced in the same manner as in Example 1 except that the suction method in the cell suction step was changed to “overall” as shown in Table 1. About the obtained separation membrane, the incidence (%) of the thick film portion was determined. The obtained separation membrane was subjected to a pervaporation test. The results are shown in Table 1.
- Examples 5 to 7 The same as in Example 1 except that the monolith substrate used had the “end face diameter”, “length in the cell extending direction”, “cell number”, and “cell diameter” as shown in Table 1.
- a separation membrane was produced by the method described above. About the obtained separation membrane, the incidence (%) of the thick film portion was determined. The obtained separation membrane was subjected to a pervaporation test. The results are shown in Table 1.
- Comparative Example 1 In Comparative Example 1, a separation membrane was manufactured by performing a drying step after the membrane forming step without performing the cell suction step. The film forming process and the drying process were the same as in Example 1. About the obtained separation membrane, the incidence (%) of the thick film portion was determined. The obtained separation membrane was subjected to a pervaporation test. The results are shown in Table 1.
- FIGS. 10 to 12 were created from the results in the examples and comparative examples.
- FIG. 10 is a graph showing the relationship between the amount of suction (%) and the ethanol permeation flow rate (kg / m 2 h) in each example and comparative example.
- FIG. 11 is a graph showing the relationship between the water permeation flow rate (kg / m 2 h) and the ethanol permeation flow rate (kg / m 2 h) in each example and comparative example.
- FIG. 12 is a graph showing the relationship between the incidence rate (%) of the thick film part and the ethanol permeation flow rate (kg / m 2 h).
- the vertical axis represents the ethanol permeation flow rate (kg / m 2 h).
- region of the separation performance of a separation membrane is shown in the relationship between water permeation
- the separation membranes obtained in Examples 1 to 7 had a low incidence of thick film portions and a uniform film thickness.
- the separation membranes obtained in Examples 1 to 7 have good water permeation flow rate and ethanol permeation flow rate in the target region of the separation performance. The separation membrane showed separation performance.
- the separation membrane obtained in Comparative Example 1 was far from the target region of the separation performance, and the separation performance was poor.
- the cause is that in the membrane formation process, an excess polyamic acid solution remains in the cell, and the drying process was performed while the excess polyamic acid solution remained. It can be considered that there were a large number of locations where the film thickness increased. That is, in the separation membrane obtained in Comparative Example 1, the rate of occurrence of the thick film portion is extremely large as compared with Examples 1 to 7, and the separation membrane is separated from the thick film portion. It is assumed that a defect such as a crack has occurred.
- the suction method by partial suction was able to reduce the occurrence rate (%) of the thick film portion as compared with the suction method by whole suction. That is, in Example 1 of the suction method by partial suction and Example 4 of the suction method by overall suction, the suction amount (%) is larger in Example 4, but the occurrence of the thick film portion is generated. The rate (%) was also high. From this, it can be considered that in the suction method using the overall suction, the surplus precursor solution was sucked preferentially from the cell having a low suction resistance. Of course, the separation performance of the separation membrane was sufficiently good even in the overall suction method.
- Example 2 where the suction time was 2 minutes, the amount of suction in the cell suction process was smaller than in the other examples.
- the generation rate of the thick film portion was increased in proportion to the suction amount.
- the diameters of the first end face and the second end face of the monolith substrate are increased, the occurrence rate of the thick film portion tends to increase accordingly.
- the separation membrane manufacturing method of the present invention the correlation between the suction time and the suction amount described above and the occurrence rate (%) of the thick film portion is recognized. It is preferable to determine the end time of the cell suction step based on the time and the suction amount.
- the present invention can be suitably used for producing a separation membrane used for separation of various mixtures such as separation of water and ethanol in the biomass field.
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Abstract
Description
本発明の分離膜の製造方法の一の実施形態は、製膜工程と、セル吸引工程と、乾燥工程と、を備えた分離膜の製造方法である。本実施形態の分離膜の製造方法は、図1に示すようなモノリス基材1のセル2の表面に、分離膜を形成する分離膜の製造方法である。図1は、本発明の分離膜の製造方法の一の実施形態に用いられるモノリス基材を模式的に示す斜視図である。
本実施形態の分離膜の製造方法においては、まず、図2に示すように、多孔質のモノリス基材1に形成されたセル2内に、分離膜の前駆体溶液を通すことにより、そのセル2の表面に、前駆体溶液からなる分離膜前駆体を形成する。この製膜工程によって、セル2の表面側に、前駆体溶液31が塗布され、セル2の表面側に、前駆体溶液31からなる分離膜前駆体が形成される。図2は、本発明の分離膜の製造方法の一の実施形態における製膜工程の一例を模式的に示す説明図である。
本実施形態の分離膜の製造方法においては、上記製膜工程の後、モノリス基材の第一の端面又は第二の端面におけるセルの開口部から、分離膜前駆体を製膜したセル内を吸引するセル吸引工程を行う。このようなセル吸引工程を設けることにより、セルの表面に部分的に厚く塗布された余剰の前駆体溶液を吸引して、均一な膜厚の分離膜前駆体を得ることができる。これにより、分離膜の厚さが部分的に厚くなる厚膜部の発生を有効に抑制することができる。
本実施形態の分離膜の製造方法においては、上記セル吸引工程の後、製膜された分離膜前駆体を乾燥する乾燥工程を行う。分離膜前駆体を乾燥する方法については特に制限はなく、従来公知の分離膜の製造方法における、乾燥方法を好適に用いることができる。例えば、図6に示すように、分離膜前駆体3を製膜したモノリス基材1のセル2内に、熱風15を通過させる通風乾燥を行って、分離膜前駆体3を乾燥させることが好ましい。分離膜前駆体3の乾燥を、通風乾燥によって行うことにより、分離膜前駆体3の表面から、分離膜前駆体3全体に均一な熱伝達をもたらしつつ、この分離膜前駆体3を良好に乾燥させることができる。このため、分離膜前駆体3全体をムラ無く均一に乾燥させることができる。ここで、図6は、本発明の分離膜の製造方法の一の実施形態における乾燥工程の一例を示す説明図である。
本実施形態の分離膜の製造方法は、乾燥工程によって乾燥させた分離膜前駆体を、熱分解して炭化させることにより分離膜を得る炭化工程を更に備えたものであってもよい。この炭化工程は、製造する分離膜が、炭素膜である場合に行われる工程である。
次に、本発明の分離膜複合体の製造方法の一の実施形態について説明する。本実施形態の分離膜複合体の製造方法によれば、第一の端面から第二の端面に延びるように複数のセルが形成された筒状の多孔質のモノリス基材と、このモノリス基材のセルの表面に配設された分離膜と、を備えた分離膜複合体を製造することができる。
次に、本発明の分離膜複合体の一の実施形態について説明する。本実施形態の分離膜複合体は、図7及び図8に示すように、多孔質のモノリス基材101と、分離膜103とを備えた分離膜複合体200である。モノリス基材101は、第一の端面111から第二の端面112に延びるように複数のセル102が形成された筒状のものである。分離膜103は、モノリス基材101に形成されたセル102の表面に配設されたものである。図7は、本発明の分離膜複合体の一の実施形態を模式的に示す斜視図である。図8は、本発明の分離膜複合体の一の実施形態の、セルの延びる方向に平行に切断した断面を模式的に示す断面図である。
まず、分離膜を製造するための基材となる、多孔質のモノリス基材を用意した。モノリス基材の材質は、アルミナとした。モノリス基材の形状は、第一の端面及び第二の端面を有する円筒状であり、この第一の端面及び第二の端面の直径が30mmで、セルの延びる方向の長さが1000mmであった。このモノリス基材には、第一の端面から第二の端面に延びるセルが、50個形成されている。セルの開口部の形状は、円形とした。1個のセルの開口部の直径は、2.5mmであった。
浸透気化試験は、図9に示すような浸透気化装置を使用して行った。図9は、実施例において、水/エタノール分離性能の評価に使用した浸透気化装置の概略図である。図9に示すように、分離膜が形成されたモノリス基材100を筒状の容器55内に収納し、モノリス基材100の両端外周部において、容器55内周面との隙間をシール材56によりシールした。恒温槽57に収容されたビーカー58内で所定温度に温められた供給液59を、循環ポンプ60により循環ライン71~73に循環させ、循環ライン71~73の途中に配された容器55内のモノリス基材100のセル内を通過させた。
セル吸引工程における吸引時間を、表1に示すように変更した以外は、実施例1と同様の方法で、分離膜を製造した。得られた分離膜について、厚膜部の発生率(%)を求めた。また、得られた分離膜について、浸透気化試験を行った。各結果を表1に示す。
セル吸引工程における吸引方法を、表1に示すように「全体的」に変更した以外は、実施例1と同様の方法で、分離膜を製造した。得られた分離膜について、厚膜部の発生率(%)を求めた。また、得られた分離膜について、浸透気化試験を行った。各結果を表1に示す。
モノリス基材として、表1に示すような「端面の直径」、「セルの延びる方向の長さ」、「セル数」、及び「セル径」のものを用いた以外は、実施例1と同様の方法で、分離膜を製造した。得られた分離膜について、厚膜部の発生率(%)を求めた。また、得られた分離膜について、浸透気化試験を行った。各結果を表1に示す。
比較例1においては、製膜工程の後、セル吸引工程を行わず、乾燥工程を行って分離膜を製造した。製膜工程、及び乾燥工程については、実施例1と同様の方法とした。得られた分離膜について、厚膜部の発生率(%)を求めた。また、得られた分離膜について、浸透気化試験を行った。各結果を表1に示す。
表1及び図12に示すように、実施例1~7にて得られた分離膜は、厚膜部の発生率が低く、膜厚が均一なものであった。また、表1、図11及び図12に示すように、実施例1~7にて得られた分離膜は、分離性能の目標領域に水透過流速とエタノール透過流速とが収まっており、良好な分離性能を示す分離膜であった。
Claims (14)
- 第一の端面から第二の端面に延びるように複数のセルが形成された筒状の多孔質のモノリス基材の前記セル内に、分離膜の前駆体溶液を通すことにより、前記セルの表面に、前記前駆体溶液からなる分離膜前駆体を形成する製膜工程と、
前記モノリス基材の前記第一の端面又は前記第二の端面における前記セルの開口部から、前記分離膜前駆体を製膜した前記セル内を吸引するセル吸引工程と、
前記セル内を吸引した前記モノリス基材の前記セルの表面に製膜された前記分離膜前駆体を乾燥させる乾燥工程と、を備えた分離膜の製造方法。 - 前記セル吸引工程において、前記モノリス基材の前記第一の端面における前記セルの開口部が鉛直方向の下向きに開口するように、前記モノリス基材を前記セルの延びる方向が鉛直となるように配置し、前記モノリス基材の前記第一の端面における前記セルの前記開口部から、前記セル内を吸引する請求項1に記載の分離膜の製造方法。
- 前記セル吸引工程において、前記モノリス基材を前記セルの延びる方向が鉛直となるように配置し、その状態を60分以下の時間保持した後に、前記モノリス基材の前記第一の端面における前記セルの前記開口部から、前記セル内を吸引する請求項2に記載の分離膜の製造方法。
- 前記製膜工程において、前記セル内に付着した前記前駆体溶液の質量に対する、前記セル吸引工程において、前記セル内から吸引される前記前駆体溶液の質量の割合が、0.5~2.5%である請求項1~3のいずれか一項に記載の分離膜の製造方法。
- 前記乾燥工程が、前記セル内に熱風を通過させる通風乾燥を行って、前記分離膜前駆体を乾燥させるものである請求項1~4のいずれか一項に記載の分離膜の製造方法。
- 前記製膜工程、前記セル吸引工程及び前記乾燥工程を一組の工程として、前記一組の工程を、2回以上繰り返して行う請求項1~5のいずれか一項に記載の分離膜の製造方法。
- 前記乾燥工程によって乾燥させた前記分離膜前駆体を、熱分解して炭化させることにより分離膜を得る炭化工程を更に備えた請求項1~6のいずれか一項に記載の分離膜の製造方法。
- 前記前駆体溶液が、ポリアミド酸溶液である請求項1~7のいずれか一項に記載の分離膜の製造方法。
- 前記乾燥工程において、前記分離膜前駆体を乾燥させるとともにイミド化させる請求項8に記載の分離膜の製造方法。
- 前記モノリス基材の外周面の少なくとも一部にシールを施した後、前記製膜工程を行う請求項1~9のいずれか一項に記載の分離膜の製造方法。
- 第一の端面から第二の端面に延びるように複数のセルが形成された筒状の多孔質のモノリス基材の前記セル内に、請求項1~10のいずれか一項に記載の分離膜の製造方法によって分離膜を作製して、前記モノリス基材と前記分離膜とを備えた分離膜複合体を製造する分離膜複合体の製造方法。
- 第一の端面から第二の端面に延びるように複数のセルが形成された筒状の多孔質のモノリス基材と、前記セルの表面に配設された分離膜と、を備え、
前記分離膜の厚さが5μm以上の厚膜部を有しない前記セルの個数の割合が、全ての前記セルの個数に対して、80%以上である分離膜複合体。 - 前記分離膜が、炭素膜である請求項12に記載の分離膜複合体。
- 前記セルの表面に配設された前記分離膜の平均厚さが、0.1~3μmである請求項12又は13に記載の分離膜複合体。
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US10213749B2 (en) | 2014-12-09 | 2019-02-26 | Ngk Insulators, Ltd. | Separation membrane structure and method for manufacturing same |
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EP2826544A4 (en) | 2015-11-18 |
JP6074410B2 (ja) | 2017-02-01 |
CN104168989A (zh) | 2014-11-26 |
JPWO2013136869A1 (ja) | 2015-08-03 |
US20140374341A1 (en) | 2014-12-25 |
EP2826544A1 (en) | 2015-01-21 |
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