WO2022163064A1 - 分離膜複合体および分離膜複合体の製造方法 - Google Patents
分離膜複合体および分離膜複合体の製造方法 Download PDFInfo
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- WO2022163064A1 WO2022163064A1 PCT/JP2021/041385 JP2021041385W WO2022163064A1 WO 2022163064 A1 WO2022163064 A1 WO 2022163064A1 JP 2021041385 W JP2021041385 W JP 2021041385W WO 2022163064 A1 WO2022163064 A1 WO 2022163064A1
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- WO
- WIPO (PCT)
- Prior art keywords
- support
- separation membrane
- dense portion
- boundary position
- slurry
- Prior art date
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- QHMQWEPBXSHHLH-UHFFFAOYSA-N sulfur tetrafluoride Chemical compound FS(F)(F)F QHMQWEPBXSHHLH-UHFFFAOYSA-N 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
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- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
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- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
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- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
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- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
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- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
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- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
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- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3214—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the method for obtaining this coating or impregnating
- B01J20/3223—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the method for obtaining this coating or impregnating by means of an adhesive agent
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
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Definitions
- the present invention relates to a separation membrane composite and a method for producing a separation membrane composite.
- a separation membrane composite in which a separation membrane is provided (supported) on a porous support has been used.
- separation is performed by selectively permeating a highly permeable substance among the supplied mixed substances through the separation membrane.
- a dense portion is provided on part of the surface of the support in order to prevent substances from moving from the space on the supply side to the space on the permeate side without permeating the separation membrane.
- a dense portion is provided at the end of the surface of the support on which the separation membrane is provided, and the separation membrane and the dense portion partially overlap on the surface.
- the dense portion covers the surface from a predetermined boundary position on the surface toward one side
- the separation film covers the surface toward the other side from the boundary position and is dense in the vicinity of the boundary position. cover the part
- Japanese Patent Application Laid-Open No. 2009-66528 Document 1
- Japanese Patent No. 5810083 Document 2
- Japanese Patent No. 4748730 discloses a method for sealing an end surface of a ceramic filter comprising a base material made of a ceramic porous body in which a large number of cells are formed and a filtration membrane formed on the inner wall surface of each cell. is disclosed.
- the slurry of the sealing material is applied to the end face of the base material in two steps of applying with a stamp and applying with a spray to a thickness of 0.2 mm or more, and a part of the slurry is applied to each edge adjacent to the end face.
- the inner wall surface of the cell is penetrated to a depth of 0.5 to 3 mm to adhere the slurry. After that, baking is performed to form a dense portion.
- Japanese Patent Application Laid-Open No. 2019-145612 (Document 4) describes a method of measuring and calculating the average roughness of the surface of the insulating substrate at the portion where the insulating substrate and the sealing resin are in close contact.
- the cross section of the insulating substrate is photographed with a scanning electron microscope to prepare an SEM image, the SEM image is binarized to prepare image data of the surface shape, and the image data is divided into two using image digitization software.
- the average roughness is obtained by converting to dimensional coordinate data and using a predetermined formula.
- the present invention is directed to a separation membrane composite, and aims to suppress the occurrence of cracks and the like in the separation membrane in the vicinity of the boundary position, and to suppress the deterioration of the separation performance of the separation membrane composite.
- a separation membrane composite comprises a porous support and, on one surface of the support, with one position in a predetermined direction as a boundary position, and a dense portion covering the surface toward one side of the support, and covering the surface from the boundary position toward the other side in the predetermined direction on the surface of the support, and the dense portion near the boundary position and a separation membrane covering the part.
- the boundary position in a cross section along the predetermined direction and perpendicular to the surface of the support to 30 ⁇ m toward the one side in the predetermined direction, a line connecting each position on the surface of the dense portion on the separation membrane side and the boundary position, and the surface of the support
- the maximum value of the four evaluation angles at the four measurement positions is 5 degrees or more and 45 degrees or less.
- the present invention it is possible to suppress the occurrence of cracks and the like in the separation membrane in the vicinity of the boundary position, and it is possible to suppress the deterioration of the separation performance of the separation membrane composite.
- the closed porosity of the dense portion is 10% or less in the range of interest of the cross section.
- the thickness of the separation membrane is 5 ⁇ m or less
- the thickness of the surface of the dense portion is calculated based on a straight line along the surface of the dense portion on the separation membrane side within the range of interest of the cross section.
- Average roughness is 0.01 ⁇ m or more and 10 ⁇ m or less.
- the separation membrane has a thickness of 5 ⁇ m or less, and the dense portion has a surface roughness Ra of 0.01 ⁇ m or more and 1 ⁇ m or less in the region where the separation membrane does not exist.
- the surface of the support is a cylindrical surface along the predetermined direction
- the four measurement positions are set circumferentially on the cylindrical surface at intervals of 90 degrees
- the four measurement positions are The size of the range of the four evaluation angles in is 15 degrees or less.
- the surface of the support is a cylindrical surface along the predetermined direction
- the boundary position is provided at an end of the support on the one side of the predetermined direction
- the dense portion is the supporting surface. It also covers the end face of said one side of the body.
- a method for producing a separation membrane composite comprises: a) on one surface of a porous support, with one position in a predetermined direction as a boundary position, b) arranging the one side end of the support in the predetermined direction downward and the other side of the support in the predetermined direction; a step of drying the slurry by drying the slurry with the end placed upward, or by blowing air along the surface from the other side of the support toward the one side; c) forming a dense portion by firing the slurry; d) covering the surface of the support from the boundary position toward the other side in the predetermined direction; and forming a separation film covering the dense portion in the vicinity of the boundary position.
- the viscosity of the slurry in the step a) is 2 dPa ⁇ s or more and 30 dPa ⁇ s or less.
- FIG. 1 is a cross-sectional view of a separation membrane composite
- FIG. FIG. 4 is a cross-sectional view showing an enlarged part of the separation membrane composite.
- FIG. 3 is an enlarged cross-sectional view showing the vicinity of one end of the separation membrane composite.
- FIG. 4 is an enlarged cross-sectional view showing the vicinity of the boundary position of the separation membrane composite.
- FIG. 4 is an enlarged cross-sectional view showing the vicinity of the boundary position of the separation membrane composite.
- FIG. 3 is a diagram showing the flow of manufacturing a separation membrane composite.
- FIG. 4 is a cross-sectional view showing a support;
- FIG. 4 is a cross-sectional view showing a separation membrane composite of a comparative example;
- FIG. 4 is a perspective view showing a support;
- FIG. 3 shows a separation device;
- FIG. 1 is a cross-sectional view of the separation membrane composite 1, showing a cross section parallel to the longitudinal direction of the support 11, which will be described later.
- FIG. 2 is a cross-sectional view showing an enlarged part of the separation membrane composite 1.
- the separation membrane composite 1 is a zeolite membrane composite, and includes a porous support 11 and a zeolite membrane 12 as a separation membrane provided on the support 11 .
- the zeolite membrane 12 is at least a membrane-like zeolite formed on the surface of the support 11, and does not include an organic membrane in which zeolite particles are simply dispersed.
- the zeolite membrane 12 may contain two or more types of zeolites having different structures and compositions.
- the zeolite membrane 12 is drawn with a thick line.
- the zeolite membrane 12 is hatched.
- the thickness of the zeolite membrane 12 is drawn thicker than it actually is.
- the separation membrane composite 1 may be other than the zeolite membrane composite, and instead of the zeolite membrane 12, an inorganic membrane formed of an inorganic substance other than zeolite or a membrane other than an inorganic membrane is used as a support as a separation membrane. 11 may be formed. A separation membrane in which zeolite particles are dispersed in an organic membrane may also be used. In the following explanation, it is assumed that the separation membrane is the zeolite membrane 12 .
- the support 11 is a porous member that is permeable to gas and liquid.
- the support 11 is a monolithic type in which a plurality of through-holes 111 extending in the longitudinal direction (that is, the left-right direction in FIG. 1) are provided in an integrally formed columnar main body. a support.
- the support 11 is substantially cylindrical.
- a cross section perpendicular to the longitudinal direction of each through-hole 111 (that is, cell) is, for example, substantially circular.
- the diameter of the through-holes 111 is drawn larger than the actual number, and the number of the through-holes 111 is drawn smaller than the actual number.
- the zeolite membrane 12 is formed on the inner peripheral surface of the through hole 111 and covers substantially the entire inner peripheral surface of the through hole 111 .
- the length of the support 11 (that is, the length in the horizontal direction in FIG. 1) is, for example, 10 cm to 200 cm.
- the outer diameter of the support 11 is, for example, 0.5 cm to 30 cm.
- the distance between the central axes of adjacent through holes 111 is, for example, 0.3 mm to 10 mm.
- the surface roughness (Ra) of the support 11 is, for example, 0.1 ⁇ m to 5.0 ⁇ m, preferably 0.2 ⁇ m to 2.0 ⁇ m.
- the shape of the support 11 may be, for example, a honeycomb shape, a flat plate shape, a tubular shape, a cylindrical shape, a columnar shape, a polygonal columnar shape, or the like. When the shape of the support 11 is tubular or cylindrical, the thickness of the support 11 is, for example, 0.1 mm to 10 mm.
- the support 11 is made of a ceramic sintered body.
- Ceramic sintered bodies selected as the material for the support 11 include, for example, alumina, silica, mullite, zirconia, titania, yttria, silicon nitride, and silicon carbide.
- support 11 contains at least one of alumina, silica and mullite.
- the support 11 may contain an inorganic binder. At least one of titania, mullite, sinterable alumina, silica, glass frit, clay mineral, and sinterable cordierite can be used as the inorganic binder.
- the average pore size of the support 11 is, for example, 0.01 ⁇ m to 70 ⁇ m, preferably 0.05 ⁇ m to 25 ⁇ m.
- the average pore size of the support 11 near the surface where the zeolite membrane 12 is formed is 0.01 ⁇ m to 1 ⁇ m, preferably 0.05 ⁇ m to 0.5 ⁇ m.
- Average pore size can be measured, for example, by a mercury porosimeter, a perm porosimeter or a nanoperm porosimeter.
- D5 is, for example, 0.01 ⁇ m to 50 ⁇ m
- D50 is, for example, 0.05 ⁇ m to 70 ⁇ m
- D95 is, for example, 0.1 ⁇ m to 2000 ⁇ m.
- the porosity of the support 11 near the surface where the zeolite membrane 12 is formed is, for example, 20% to 60%.
- the support 11 has, for example, a multi-layer structure in which multiple layers with different average pore diameters are laminated in the thickness direction.
- the average pore size and sintered grain size in the surface layer including the surface on which the zeolite membrane 12 is formed are smaller than the average pore size and sintered grain size in layers other than the surface layer.
- the average pore diameter of the surface layer of the support 11 is, for example, 0.01 ⁇ m to 1 ⁇ m, preferably 0.05 ⁇ m to 0.5 ⁇ m.
- the above materials can be used for each layer.
- the materials of the multiple layers forming the multilayer structure may be the same or different.
- the zeolite membrane 12 is a porous membrane having fine pores (micropores).
- the zeolite membrane 12 can be used as a separation membrane that separates a specific substance from a mixed substance in which a plurality of types of substances are mixed, using molecular sieve action.
- the zeolite membrane 12 is less permeable to other substances than the specific substance. In other words, the permeation amount of the other substance through the zeolite membrane 12 is smaller than the permeation amount of the specific substance.
- the thickness of the zeolite membrane 12 is, for example, 0.05 ⁇ m to 30 ⁇ m, preferably 0.1 ⁇ m to 20 ⁇ m, more preferably 0.5 ⁇ m to 10 ⁇ m. Separation performance is improved by increasing the thickness of the zeolite membrane 12 . Thinning the zeolite membrane 12 increases the permeation rate.
- the surface roughness (Ra) of the zeolite membrane 12 is, for example, 5 ⁇ m or less, preferably 2 ⁇ m or less, more preferably 1 ⁇ m or less, and even more preferably 0.5 ⁇ m or less.
- the average pore diameter of the zeolite membrane 12 is, for example, 1 nm or less.
- the average pore diameter of the zeolite membrane 12 is preferably 0.2 nm or more and 0.8 nm or less, more preferably 0.3 nm or more and 0.5 nm or less, still more preferably 0.3 nm or more and 0.5 nm or less. 4 nm or less.
- the average pore diameter of the zeolite membrane 12 is smaller than the average pore diameter of the support 11 in the vicinity of the surface where the zeolite membrane 12 is formed.
- the average pore diameter is the arithmetic mean of the short diameter and the long diameter of the n-membered ring pores.
- An n-membered ring pore is a pore in which the number of oxygen atoms in a portion forming a ring structure in which an oxygen atom is bonded to a T atom is n.
- the zeolite has a plurality of n-membered ring pores with the same n
- the arithmetic mean of the short diameter and the long diameter of all the n-membered ring pores is taken as the average pore diameter of the zeolite.
- the average pore diameter of a zeolite membrane is uniquely determined by the skeletal structure of the zeolite. iza-structure. It can be obtained from the values disclosed in org/databases/>.
- the type of zeolite constituting the zeolite membrane 12 is not particularly limited, but examples include AEI, AEN, AFN, AFV, AFX, BEA, CHA, DDR, ERI, ETL, and FAU types ( X-type, Y-type), GIS-type, KFI-type, LEV-type, LTA-type, MEL-type, MER-type, MFI-type, MOR-type, PAU-type, RHO-type, SAT-type, SOD-type zeolite.
- the maximum number of membered rings of the zeolite is preferably 8 or less (eg, 6 or 8).
- the zeolite membrane 12 is, for example, DDR type zeolite.
- the zeolite membrane 12 is a zeolite membrane made of zeolite whose structure code is "DDR" as defined by the International Zeolite Society.
- the zeolite constituting the zeolite membrane 12 has an intrinsic pore diameter of 0.36 nm ⁇ 0.44 nm and an average pore diameter of 0.40 nm.
- the zeolite membrane 12 contains, for example, silicon (Si).
- the zeolite membrane 12 may contain, for example, any two or more of Si, aluminum (Al) and phosphorus (P).
- the zeolite constituting the zeolite membrane 12 is a zeolite in which the atoms (T atoms) located at the center of the oxygen tetrahedron (TO 4 ) constituting the zeolite are Si only, or are composed of Si and Al, and T atoms.
- AlPO-type zeolite composed of Al and P SAPO-type zeolite T atoms composed of Si, Al and P
- MAPSO-type zeolite T atoms composed of magnesium (Mg), Si, Al and P
- T A ZnAPSO type zeolite or the like composed of zinc (Zn), Si, Al, and P atoms can be used. Some of the T atoms may be substituted with other elements.
- the Si/Al ratio in the zeolite membrane 12 is, for example, 1 or more and 100,000 or less.
- the Si/Al ratio is preferably 5 or more, more preferably 20 or more, still more preferably 100 or more, and the higher the better.
- the Si/Al ratio in the zeolite membrane 12 can be adjusted by adjusting the mixing ratio of the Si source and the Al source in the raw material solution, which will be described later.
- the zeolite membrane 12 may contain an alkali metal.
- the alkali metal is, for example, sodium (Na) or potassium (K).
- the permeance of CO 2 through the zeolite membrane 12 at 20° C. to 400° C. is, for example, 100 nmol/m 2 ⁇ s ⁇ Pa or more.
- the CO 2 permeation amount/CH 4 leakage amount ratio (permeance ratio) of the zeolite membrane 12 at 20° C. to 400° C. is, for example, 100 or more.
- the permeance and permeance ratio are for a CO 2 partial pressure difference of 1.5 MPa between the feed side and the permeate side of the zeolite membrane 12 .
- FIG. 3 is an enlarged view showing the vicinity of one end of the separation membrane composite 1 of FIG.
- the dense portion 13 is provided at each end of the support 11 in the longitudinal direction.
- illustration of parallel oblique lines in the cross section of the dense portion 13 is omitted (the same applies to other drawings).
- the dense portion 13 connects a region other than the through holes 111 on the end face of the support 11, a region near the end face on the outer peripheral surface of the support 11, and a region near the end face on the inner peripheral face of each through hole 111. cover effectively.
- Dense portion 13 seals these areas in support 11 .
- Dense portion 13 is a seal that prevents the inflow and outflow of gas from the region.
- the longitudinal length of the dense portion 13 on the outer peripheral surface of the support 11 and the inner peripheral surface of the through-hole 111 is, for example, 0.1 to 5.0 cm.
- the dense portion 13 is made of glass or resin, for example. Both longitudinal ends of each through-hole 111 are not covered with the dense portion 13, and gas can flow into and out of the through-hole 111 from both ends.
- a position near the end surface of the support 11 is defined as a boundary position P1
- the dense portion 13 extends from the boundary position P1 to the end surface in the longitudinal direction. side to cover the inner peripheral surface.
- the boundary position P1 is the tip position of the dense portion 13 inside the through hole 111 .
- FIG. 3 only some boundary positions P1 are indicated by black dots.
- the boundary position P1 in the longitudinal direction is substantially constant over the entire circumference in the circumferential direction perpendicular to the longitudinal direction (circumferential direction of the inner peripheral surface). may vary somewhat along
- the boundary positions P1 in the longitudinal direction of the plurality of through holes 111 are preferably substantially constant, but may differ to some extent.
- the already-described zeolite membrane 12 covers substantially the entire area between the dense portions 13 provided at both ends of the support 11 on the inner peripheral surface of each through-hole 111 .
- the zeolite membrane 12 covers the inner peripheral surface from the boundary position P1 of each dense portion 13 toward the side opposite to the dense portion 13 in the longitudinal direction.
- the entire inner peripheral surface of through-hole 111 is covered with dense portion 13 or zeolite membrane 12 .
- the zeolite membrane 12 also covers the dense portion 13 in the vicinity of the boundary position P1.
- a composite portion where the dense portion 13 and the zeolite membrane 12 overlap is provided in the vicinity of the boundary position P1.
- the length of the portion (composite portion) where the dense portion 13 and the zeolite membrane 12 overlap is, for example, 50 ⁇ m or less, preferably 10 ⁇ m or less.
- FIG. 4 is an enlarged view showing the vicinity of the boundary position P1 of the separation membrane composite 1 in FIG. 4 shows a cross section along the longitudinal direction and perpendicular to the inner peripheral surface of the through hole 111, as in FIGS.
- the thickness of dense portion 13 gradually increases along the inner peripheral surface of through-hole 111 from boundary position P 1 toward the end surface of support 11 .
- the slope of the surface of the dense portion 13 is gentle in the vicinity of the boundary position P1.
- the surface roughness (unevenness) of the dense portion 13 is small, that is, the surface of the dense portion 13 is smooth.
- the dense portion 13 is covered with the zeolite membrane 12 in the vicinity of the boundary position P1. Since the inclination of the surface of the dense portion 13 in the vicinity of the boundary position P1 is gentle, the angle at which the zeolite membrane 12 bends at the boundary position P1 also becomes small, and cracks occur in the zeolite membrane 12 due to stress concentration or the like (for example, due to heating). Cracks caused by the generated stress) are suppressed. In addition, since the surface roughness of the dense portion 13 in the vicinity of the boundary position P1 is small, the generation of defects (such as holes) in the dense portion 13 and the zeolite membrane 12 formed on the dense portion 13 is suppressed. be.
- an SEM image is obtained by imaging the cross section of the separation membrane composite 1 shown in FIG. 4 with a SEM (scanning electron microscope). The magnification of the SEM image is, for example, 5000 times. Subsequently, in the SEM image, a range of interest R1 (indicated by an arrow in FIG. 4), which is a longitudinal range of 30 ⁇ m from the boundary position P1 toward the end surface of the support 11, is set.
- the angle formed by the line connecting each position on the surface of the dense portion 13 on the zeolite membrane 12 side and the boundary position P1 and the inner peripheral surface of the through hole 111 (hereinafter, “from the boundary position P1 ) is obtained as the evaluation angle ⁇ .
- the elevation angle from the boundary position P1 is substantially constant at any position within the attention range R1.
- the example of FIG. 5 is for explaining the measurement of the evaluation angle ⁇ , and the actual surface of the dense portion 13 does not have large unevenness as shown in FIG. 5 .
- illustration of the zeolite membrane 12 is omitted. If the evaluation angle ⁇ can be obtained appropriately, it is not necessary to obtain elevation angles from the boundary position P1 for all positions on the surface of the dense portion 13 within the attention range R1.
- the dense portion 13 and the zeolite membrane 12 are formed on the inner peripheral surface of the through hole 111, which is a cylindrical surface along the longitudinal direction.
- the evaluation angles ⁇ are obtained for each of the four measurement positions set (evenly) at intervals of 90 degrees in the circumferential direction on the cylindrical surface.
- the four evaluation angles ⁇ at the four measurement positions are obtained. is 5 degrees or more and 45 degrees or less.
- the upper limit of the maximum value of the evaluation angle ⁇ is preferably 43 degrees, more preferably 40 degrees.
- the smaller the maximum value of the evaluation angle ⁇ the smaller the bending angle of the zeolite membrane 12 in the vicinity of the boundary position P1.
- the evaluation angle ⁇ is 5 degrees or more, it is possible to prevent the dense portion 13 from becoming excessively thin and causing defects in the vicinity of the boundary position P1.
- the size of the range of the four evaluation angles ⁇ at the four measurement positions that is, the difference between the maximum and minimum values of the four evaluation angles ⁇ is, for example, 15 degrees or less. It can be said that the smaller the size of the range of the four evaluation angles ⁇ , the smaller the variation in the shape of the dense portion 13 in the circumferential direction.
- the size of the range of the four evaluation angles ⁇ is preferably 12 degrees or less, more preferably 10 degrees or less.
- the measurement of the surface roughness of the dense portion 13 in the vicinity of the boundary position P1 is performed, for example, according to the method disclosed in Japanese Patent Application Laid-Open No. 2019-145612 (Document 4 above).
- an SEM image showing the cross section of the separation membrane composite 1 is acquired in the same manner as in the measurement of the evaluation angle ⁇ .
- the same SEM image as for measuring the evaluation angle ⁇ may be used.
- a straight line L1 is set along the surface of the dense portion 13 on the zeolite membrane 12 (not shown in FIG. 5) side in the attention range R1.
- two-dimensional coordinate data indicating the shape of the surface is acquired from the SEM image, and an approximate straight line of the shape of the surface within the attention range R1 is obtained as a straight line L1 by the method of least squares or the like using the two-dimensional coordinate data. Desired. After that, the roughness Za of the surface of the dense portion 13 is obtained by Equation (1).
- Equation 1 Zn is the difference between the two-dimensional coordinate data at each position n within the attention range R1 in the longitudinal direction and the straight line L1.
- N is a value obtained by dividing the 30 ⁇ m width of the attention range R1 by the calculated pitch.
- the calculated pitch is 0.01 ⁇ m, for example, and N is 3000 in this case.
- the surface roughness Za of the dense portion 13 is calculated with reference to the straight line L1 along the surface of the dense portion 13 on the zeolite membrane 12 side within the attention range R1.
- the average value of the roughness Za obtained at a plurality of measurement positions that is, the average roughness Za is 0.01 ⁇ m or more and 10 ⁇ m or less. is preferred.
- the upper limit of the range of the average roughness Za is more preferably 5 ⁇ m, still more preferably 3 ⁇ m. This suppresses the generation of defects (such as holes) in the dense portion 13 and the zeolite membrane 12 formed on the dense portion 13 .
- the lower limit of the average roughness Za is more preferably 0.05 ⁇ m, still more preferably 0.1 ⁇ m. As a result, the adhesion of the zeolite film 12 formed on the dense portion 13 is increased, and the occurrence of peeling is suppressed.
- the measurement of the roughness of the surface of the dense portion 13 may be performed in a region where the zeolite membrane 12 does not exist outside the range of interest R1.
- the surface roughness Ra of the dense portion 13 in the region where the zeolite membrane 12 does not exist is measured at multiple locations on the surface of the dense portion 13 using, for example, a general-purpose three-dimensional surface structure analyzer (eg, NewView7300 manufactured by ZYGO). and obtained as an average value of a plurality of surface roughnesses Ra.
- the surface roughness Ra of one spot on the surface may be treated as the surface roughness Ra of the dense portion 13 as it is.
- the surface roughness Ra of the dense portion 13 is, for example, 0.01 ⁇ m or more and 1 ⁇ m or less.
- the upper limit of the range of surface roughness Ra is preferably 0.8 ⁇ m, more preferably 0.6 ⁇ m.
- the surface roughness Ra has a correlation with the average roughness Za. occurrence is suppressed.
- the closed porosity of the dense portion 13 is preferably 10% or less, more preferably 8% or less, within the attention range R1 of the cross section shown in FIG. This suppresses the occurrence of cracks originating from closed pores.
- the closed porosity in the dense portion 13 may be 0%.
- the area of the dense portion 13 and the area of the closed pores within the range of interest R1 are calculated, and the area of the closed pores is divided by the area of the dense portion 13. , the closed porosity (area ratio of closed pores) in the SEM image is obtained.
- the closed porosity in the dense portion 13 is preferably obtained as an average value of closed porosities in a plurality of SEM images.
- the support 11 is prepared (step S11).
- a monolithic support 11 is prepared.
- the support 11 is provided with a plurality of through holes 111 each extending in the longitudinal direction (that is, the vertical direction in FIG. 7).
- a slurry is prepared, for example, by adding an organic binder to the glass powder, adding water, and mixing.
- the slurry for forming the dense portion is prepared by vacuum degassing the slurry (step S12). The viscosity of the dense portion-forming slurry at 20° C.
- the viscosity of the slurry can be measured using, for example, an ultrasonic desktop viscometer (FCV-100H manufactured by Fuji Kogyo Co., Ltd.).
- FCV-100H manufactured by Fuji Kogyo Co., Ltd.
- a thickening agent or leveling agent may be added to the slurry if desired. Ceramic particles or the like may be mixed in the dense portion-forming slurry.
- one end of the support 11 in the longitudinal direction is arranged downward, and the other end is arranged upward, that is, the through hole 111 is arranged vertically.
- the support 11 is held in a substantially parallel vertical posture.
- One end (lower end) of the support 11 is immersed in the slurry for forming the dense portion in the container 91 .
- the support 11 is pulled up from the slurry at a predetermined speed (for example, 1 cm/s).
- the slurry is applied (step S13).
- one position in the longitudinal direction on the inner peripheral surface is defined as a boundary position P1, and one side of the longitudinal direction from the boundary position P1 (this Slurry for dense portion formation is applied so as to cover the inner peripheral surface toward the end face).
- the slurry is applied by immersing the end portion of the vertically oriented support 11 in the slurry, but the slurry may be applied by other methods.
- the support 11 When the support 11 is pulled up from the dense portion-forming slurry, it is held in a state in which one end is placed downward and the other end is placed upward (vertical orientation). Drying of the slurry adhering to the edge of the side is performed (step S14). Alternatively, the slurry is dried by blowing air or the like along the inner peripheral surface of the support 11 from the other side to the one side.
- the blowing speed is, for example, 1 to 30 m/s, preferably 5 to 20 m/s, and 15 m/s in this processing example. In this way, the slurry on the inner peripheral surface of the through-hole 111 is stretched from the boundary position P1 toward one side (the end surface side) in the longitudinal direction by its own weight and/or air blow.
- the support 11 does not necessarily have to be supported in a vertical posture, and the support can be held in an arbitrary posture such as a sideways posture in which the through holes 111 are substantially parallel to the horizontal direction. 11 may be supported.
- the other end of the support 11 is also coated with the slurry for forming the dense portion, and then dried.
- the support 11 is placed in a firing furnace, and the slurry on both ends is fired (step S15). Firing of the slurry is performed, for example, in an air atmosphere.
- the support 11 is supported in a lateral posture during firing of the slurry, but may be supported in any posture.
- the firing temperature is, for example, 450 to 1200.degree. C., and is 1000.degree. C. in this processing example.
- the rate of temperature increase/decrease is, for example, 100° C./h.
- the baking time is, for example, 1 to 50 hours, and is 3 hours in this processing example.
- Dense portions 13 are formed at both end portions of the support 11 by the above processing. When the slurry for forming the dense portion contains glass powder, the dense portion 13 becomes the glass seal portion.
- seed crystals used for forming the zeolite membrane 12 are prepared.
- DDR-type zeolite powder is produced by hydrothermal synthesis, and seed crystals are obtained from the zeolite powder.
- the zeolite powder may be used as it is as a seed crystal, or the seed crystal may be obtained by processing the powder by pulverization or the like.
- the support 11 is immersed in the dispersion liquid in which the seed crystals are dispersed to adhere the seed crystals to the support 11 (step S16).
- the seed crystals are adhered to the support 11 by contacting a portion of the support 11 on which the zeolite membrane 12 is to be formed with a dispersion liquid in which the seed crystals are dispersed.
- a seed crystal-attached support is produced.
- seed crystals adhere to the regions between the dense portions 13 at both ends of the inner peripheral surface of each through-hole 111 .
- the seed crystal also adheres to the dense portion 13 in the vicinity of the boundary position P1.
- areas where the zeolite membrane 12 is not desired to be formed may be masked or the like.
- the seed crystal may be attached to support 11 by other techniques.
- the support 11 to which the seed crystals are attached is immersed in the raw material solution.
- the raw material solution is prepared, for example, by dissolving or dispersing a Si source and a structure-directing agent (hereinafter also referred to as "SDA") in a solvent.
- SDA structure-directing agent
- the solvent of the raw material solution for example, water or alcohol such as ethanol is used.
- the SDA contained in the raw material solution is, for example, an organic substance.
- SDA for example, 1-adamantanamine or the like can be used.
- DDR type zeolite is grown using the seed crystals as nuclei by hydrothermal synthesis, thereby forming DDR type zeolite membrane 12 on support 11 (step S17).
- the temperature during hydrothermal synthesis is preferably 120 to 200°C.
- the hydrothermal synthesis time is preferably 6 to 100 hours.
- the zeolite membrane 12 covers the inner peripheral surface from the boundary position P1 toward the side opposite to the dense portion 13, and also covers the dense portion 13 in the vicinity of the boundary position P1.
- the support 11 and the zeolite membrane 12 are washed with pure water.
- the washed support 11 and zeolite membrane 12 are dried at 80° C., for example.
- the zeolite membrane 12 is heat-treated in an oxidizing gas atmosphere to burn off the SDA in the zeolite membrane 12 (step S18).
- SDA is almost completely removed.
- the heating temperature for removing SDA is, for example, 300-700.degree.
- the heating time is, for example, 5 to 200 hours.
- the oxidizing gas atmosphere is an atmosphere containing oxygen, such as the air.
- FIG. 8 is a cross-sectional view showing a separation membrane composite 8 of a comparative example.
- the slurry for forming the dense portion is applied to one end of the support 81, and then in step S14, the through holes 811 are formed. Drying of the slurry is carried out in a sideways position parallel to the horizontal direction. In addition, ventilation along the inner peripheral surface is not performed.
- the processing of other steps S11, S12, S15-S18 is the same as that of the separation membrane composite 1 production.
- the portion of the dense portion 83 that adheres to the region that faces downward during drying of the slurry has a shape that hangs downward under the influence of gravity. Become. Therefore, the cross-sectional shape of the dense portion 83 in the vicinity of the boundary position P1 varies greatly along the circumferential direction of the inner peripheral surface.
- the evaluation angle ⁇ see FIG. 5
- the four measurement angles ⁇ at the positions vary greatly, and the maximum value of the evaluation angles ⁇ is greater than 45 degrees.
- the zeolite film 82 bends at a large angle near the boundary position P1, and cracks and the like are likely to occur in the zeolite film 82 due to stress concentration and the like. As a result, the separation performance of the separation membrane composite 8 is degraded.
- the unevenness of the surface of the dense portion 83 in the vicinity of the boundary position P1 tends to increase, and the dense portion 83 and the zeolite membrane 82 formed on the dense portion 83 have defects. (holes, etc.) are likely to occur. In this case as well, the separation performance of the separation membrane composite 8 is degraded.
- the cross-sectional shape of the dense portion 83 varies greatly along the circumferential direction of the inner peripheral surface, the position in the circumferential direction where the thickness of the dense portion 83 on the inner peripheral surface is approximately the maximum is 4. preferably included in each measurement position.
- the separation membrane composite 1 when the evaluation angle ⁇ is obtained for each of the four measurement positions set at intervals of 90 degrees in the circumferential direction on the inner peripheral surface of the through-hole 111, the four is 5 degrees or more and 45 degrees or less. This reduces the bending angle of the zeolite membrane 12 in the vicinity of the boundary position P1. As a result, it is possible to suppress the occurrence of cracks or the like in the zeolite membrane 12 in the vicinity of the boundary position P1, and it is possible to suppress the deterioration of the separation performance of the separation membrane composite 1.
- the size of the range of the four evaluation angles ⁇ at the four measurement positions is 15 degrees or less.
- the size of the range of the four evaluation angles ⁇ at the four measurement positions may be larger than 15 degrees.
- the average roughness Za of the surface of the dense portion 13 calculated based on the straight line L1 along the surface of the dense portion 13 on the zeolite membrane 12 side is 0. .01 ⁇ m or more and 10 ⁇ m or less.
- the thickness of the zeolite membrane 12 may be greater than 5 ⁇ m (same below).
- the surface roughness Ra of the dense portion 13 in the non-existent region of the zeolite membrane 12 is preferably 0.01 ⁇ m or more and 1 ⁇ m or less.
- the surface roughness Ra of the dense portion 13 in the non-existent region of the zeolite membrane 12 is preferably 0.01 ⁇ m or more and 1 ⁇ m or less.
- the closed porosity of the dense portion 13 is 10% or less within the attention range R1.
- the boundary position P1 is provided at one end of the support 11 in the longitudinal direction, and the dense portion 13 also covers the end face of the support 11 on one side.
- the dense portion 13 may not be provided on the end face of the support 11 .
- one position in the longitudinal direction is defined as a boundary position P1, and the inner peripheral surface is covered from the boundary position P1 toward one side in the longitudinal direction.
- a slurry for forming a dense portion is applied to the .
- the viscosity of the dense portion-forming slurry is 2 dPa ⁇ s or more and 30 dPa ⁇ s or less.
- the slurry is dried with one end of the support 11 in the longitudinal direction arranged on the lower side and the other end on the upper side. The slurry is dried by blowing air along the inner peripheral surface toward the side. Then, the dense portion 13 is formed by firing the slurry.
- the zeolite membrane 12 is formed to cover the inner peripheral surface from the boundary position P1 toward the other side in the longitudinal direction and to cover the dense portion 13 in the vicinity of the boundary position P1. This makes it possible to easily manufacture the separation membrane composite 1 capable of suppressing the occurrence of cracks or the like in the zeolite membrane 12 in the vicinity of the boundary position P1.
- Example 1 methyl cellulose was added as an organic binder to glass powder having an average particle size of 10 ⁇ m, which was the material for the dense part, and water was further added and mixed to obtain a slurry.
- a slurry for forming a dense portion was prepared by degassing the slurry in a vacuum desiccator for 1 hour while stirring.
- the viscosity of the dense portion forming slurry at 20° C. was 2 dPa ⁇ s.
- An ultrasonic desktop viscometer FCV-100H manufactured by Fuji Kogyo Co., Ltd.
- FCV-100H manufactured by Fuji Kogyo Co., Ltd.
- the lower end portion of the support was immersed in the slurry for forming the dense portion in a vertical posture in which the through-holes of the support were substantially parallel to the vertical direction. After that, the support was pulled up at a speed of 1 cm/s. After applying the slurry, the slurry was dried at room temperature for 24 hours while the support was held in the same posture (vertical posture). After completion of drying, the support was placed in an electric furnace and the slurry was fired in an air atmosphere to form a dense portion as a glass seal portion. The firing conditions were 1000° C. for 3 hours, and the rate of temperature increase/decrease was 100° C./h.
- Example 2 was the same as Example 1, except that the amount of methyl cellulose added was increased and the viscosity of the slurry for forming the dense portion was set to 10 dPa ⁇ s.
- Example 3 was the same as Example 1, except that the amount of methyl cellulose added was further increased and the viscosity of the dense portion-forming slurry was changed to 30 dPa ⁇ s.
- Example 4 after the slurry for forming the dense portion was applied, air was blown from the upper end to the lower end at a speed of 15 m/s while the support was held in the same posture (vertical posture). , dried the slurry. Other treatments were the same as in Example 2.
- Example 5 after the slurry for forming the dense portion was applied, the support was placed in a horizontal posture, and the air blowing speed was 15 m/s from the end where the slurry was not applied toward the end where the slurry was applied. was blown to dry the slurry.
- Other treatments were the same as in Example 2.
- Example 6 was the same as Example 1, except that 0.1% of an antifoaming agent (KM-73, manufactured by Shin-Etsu Chemical Co., Ltd.) was added without performing vacuum degassing when preparing the slurry for forming the dense part. and
- an antifoaming agent KM-73, manufactured by Shin-Etsu Chemical Co., Ltd.
- methyl cellulose was added as an organic binder to glass powder having an average particle size of 10 ⁇ m, which was the material for the dense portion, and water was added and mixed to obtain a slurry.
- a slurry for forming a dense portion was prepared by degassing the slurry in a vacuum desiccator for 1 hour while stirring. The viscosity of the dense portion-forming slurry was 2 dPa ⁇ s. Subsequently, the lower end of the vertically oriented alumina porous support was immersed in the slurry for forming the dense portion, and then the support was pulled up at a speed of 1 cm/s.
- the support was placed on its side and the slurry was allowed to dry at room temperature for 24 hours. After completion of drying, the support was placed in an electric furnace and the slurry was fired in an air atmosphere to form a dense portion.
- the firing conditions were 1000° C. for 3 hours, and the rate of temperature increase/decrease was 100° C./h.
- a slurry for forming the dense portion was prepared by adding ethanol to glass powder having an average particle size of 10 ⁇ m, which is the material for the dense portion, and mixing. Subsequently, the lower end of the vertically oriented support was immersed in the dense portion-forming slurry, and then the support was pulled up at a speed of 1 cm/s. After the slurry was applied, the slurry was dried at room temperature for 1 hour while the support was held in the same posture (vertical posture). After completion of drying, the support was placed in an electric furnace and the slurry was fired in an air atmosphere to form a dense portion. The firing conditions were 1000° C. for 3 hours, and the rate of temperature increase/decrease was 100° C./h.
- Comparative Example 3 was the same as Comparative Example 1, except that the average particle size of the glass powder was 20 ⁇ m.
- Comparative Example 4 was the same as Comparative Example 1, except that the added amount of methyl cellulose was increased and the viscosity of the dense portion-forming slurry was changed to 40 dPa ⁇ s.
- Table 1 shows the measurement results for the dense part.
- Table 1 also shows the viscosity of the dense portion-forming slurry and the posture of the support during drying of the slurry.
- the evaluation angle was measured with respect to the dense portion 13 formed on the outer peripheral surface of the support 11a in FIG.
- a cross section of the support 11a along the longitudinal direction is imaged with a SEM (scanning electron microscope) for each of four measurement positions set at intervals of 90 degrees in the circumferential direction on the outer peripheral surface, which is a cylindrical surface. got the image.
- the magnification of the SEM image was 1000 times.
- the attention range R1 was set up to 30 ⁇ m from the boundary position P1, which is the tip of the dense portion 13, toward the longitudinal end face side.
- Maximum value of evaluation angle indicates the maximum value of the four evaluation angles at the four measurement positions. In Examples 1 to 6, the maximum evaluation angle was 5 degrees or more and 45 degrees or less, more specifically, 10 degrees or more and 40 degrees or less. On the other hand, in Comparative Examples 1 to 4, the maximum evaluation angle was greater than 45 degrees.
- Evaluation angle range in Table 1 indicates the size of the four evaluation angle ranges at the four measurement positions. In Examples 1 to 6, the evaluation angle range was 15 degrees or less, and in all cases other than Example 5, the evaluation angle range was less than 10 degrees. On the other hand, in Comparative Examples 1 to 4, the evaluation angle range was 10 degrees or more.
- Average roughness Za in Table 1 was measured by the method described above with reference to FIG. Specifically, first, an SEM image showing a cross section of the support 11a was acquired in the same manner as the measurement of the evaluation angle. Subsequently, a straight line L1 was set along the surface of the dense portion 13 (corresponding to the interface between the dense portion 13 and the zeolite membrane 12) within the attention range R1. Then, the roughness Za of the surface of the dense portion 13 was determined by Equation 1, and the average value of the roughness Za at the four measurement positions was taken as the average roughness Za. In Examples 1 to 6, the average roughness Za was 0.01 ⁇ m or more and 10 ⁇ m or less, more specifically, 3 ⁇ m or less. On the other hand, in Comparative Examples 1 to 4, except for Comparative Example 1, the average roughness Za was 2 ⁇ m or more, and in Comparative Examples 3 and 4, the average roughness Za was 5 ⁇ m or more.
- the area of the dense portion 13 and the area of the closed pores within the target range R1 were calculated in the SEM image showing the cross section of the support 11a, and the area of the closed pores was calculated. By dividing by the area of the dense portion 13, the closed porosity in the SEM image was obtained.
- the closed porosity of the dense portion 13 was determined by averaging the closed porosity of the 10 SEM images. In Examples 1 to 6 and Comparative Examples 1 to 4, the closed porosity of the dense portion 13 was less than 10%.
- the surface roughness Ra of the dense portion 13 was also measured at a position distant from the boundary position P1 (corresponding to the non-existing region of the zeolite membrane 12).
- a general-purpose three-dimensional surface structure analyzer (NewView 7300, manufactured by ZYGO) was used, the magnification of the objective lens was 50 times, and the zoom was 1 time.
- the thickness Ra was measured.
- the average value of the ten surface roughnesses Ra was taken as the surface roughness Ra of the dense portion 13 .
- the surface roughness Ra of the dense portion 13 was 0.01 ⁇ m or more and 1 ⁇ m or less.
- zeolite membranes were formed on the supports 11a of Examples 1-6 and Comparative Examples 1-4.
- seed crystals of DDR type zeolite were attached to the outer peripheral surface of the support 11a.
- a stock solution was then prepared by mixing silica, 1-adamantaneamine, ethylenediamine, and water. The weight ratio of each component in the raw material solution was 1:10:0.25:100.
- the raw material solution (membrane-forming sol) is put in and heat-treated (hydrothermal Synthesis: 130° C., 24 hours) to form a high silica DDR type zeolite membrane.
- the support 11a was heated to 450° C. in an electric furnace and held for 50 hours to burn off 1-adamantaneamine to obtain a DDR type zeolite membrane.
- the separation performance of the support 11a (that is, the separation membrane composite) on which the zeolite membrane was formed was measured.
- the gas concentrations on the feed side and the permeate side across the zeolite membrane were measured.
- the separation performance ⁇ was calculated.
- Table 1 shows the calculation results of the separation performance. Note that the separation performance in Table 1 is a value normalized based on a predetermined value. In the separation membrane composites of Examples 1-6, sufficiently high separation performance was obtained as compared with the separation membrane composites of Comparative Examples 1-4. Observation of the cross section of the separation membrane composite of the comparative example by SEM confirmed the occurrence of cracks in the zeolite membrane.
- FIG. 10 is a diagram showing the separation device 2. As shown in FIG.
- a mixed substance containing multiple types of fluids that is, gas or liquid
- a highly permeable substance in the mixed substance is permeated through the separation membrane composite 1.
- separated from the mixture by Separation in the separation device 2 may be performed, for example, for the purpose of extracting a highly permeable substance from a mixed substance, or for the purpose of concentrating a less permeable substance.
- the mixed substance (that is, mixed fluid) may be a mixed gas containing multiple types of gas, a mixed liquid containing multiple types of liquid, or a gas-liquid two-phase mixture containing both gas and liquid. It may be a fluid.
- Mixed substances include, for example, hydrogen (H 2 ), helium (He), nitrogen (N 2 ), oxygen (O 2 ), water (H 2 O), water vapor (H 2 O), carbon monoxide (CO), Carbon dioxide ( CO2 ), Nitrogen oxides, Ammonia ( NH3 ), Sulfur oxides, Hydrogen sulfide ( H2S ), Sulfur fluoride, Mercury (Hg), Arsine (AsH3) , Hydrogen cyanide (HCN), Sulfide Contains one or more of carbonyls (COS), C1-C8 hydrocarbons, organic acids, alcohols, mercaptans, esters, ethers, ketones and aldehydes.
- COS Hydrogen cyanide
- Nitrogen oxides are compounds of nitrogen and oxygen. Nitrogen oxides mentioned above include, for example, nitric oxide (NO), nitrogen dioxide (NO 2 ), nitrous oxide (also referred to as dinitrogen monoxide) (N 2 O), dinitrogen trioxide (N 2 O 3 ), dinitrogen tetroxide (N 2 O 4 ), dinitrogen pentoxide (N 2 O 5 ), and other gases called NO x (nox).
- NO nitric oxide
- NO 2 nitrogen dioxide
- NO 2 O nitrous oxide
- N 2 O 3 dinitrogen trioxide
- N 2 O 4 dinitrogen tetroxide
- N 2 O 5 dinitrogen pentoxide
- Sulfur oxides are compounds of sulfur and oxygen.
- the above sulfur oxides are gases called SOx ( socks) such as sulfur dioxide ( SO2) and sulfur trioxide (SO3).
- Sulfur fluoride is a compound of fluorine and sulfur.
- C1-C8 hydrocarbons are hydrocarbons having 1 or more and 8 or less carbons.
- the C3-C8 hydrocarbons may be straight chain compounds, side chain compounds and cyclic compounds.
- C2 to C8 hydrocarbons include saturated hydrocarbons (that is, those in which double bonds and triple bonds are not present in the molecule), unsaturated hydrocarbons (that is, those in which double bonds and/or triple bonds are present in the molecule). existing within).
- the organic acids mentioned above are carboxylic acids, sulfonic acids, and the like.
- Carboxylic acids are, for example, formic acid (CH 2 O 2 ), acetic acid (C 2 H 4 O 2 ), oxalic acid (C 2 H 2 O 4 ), acrylic acid (C 3 H 4 O 2 ) or benzoic acid (C 6 H 5 COOH) and the like.
- Sulfonic acid is, for example, ethanesulfonic acid (C 2 H 6 O 3 S).
- the organic acid may be a chain compound or a cyclic compound.
- the aforementioned alcohols are, for example, methanol (CH 3 OH), ethanol (C 2 H 5 OH), isopropanol (2-propanol) (CH 3 CH(OH)CH 3 ), ethylene glycol (CH 2 (OH)CH 2 (OH)) or butanol ( C4H9OH ), and the like.
- Mercaptans are organic compounds having hydrogenated sulfur (SH) at the end, and are also called thiols or thioalcohols.
- the mercaptans mentioned above are, for example, methyl mercaptan (CH 3 SH), ethyl mercaptan (C 2 H 5 SH) or 1-propanethiol (C 3 H 7 SH).
- esters are, for example, formate esters or acetate esters.
- ethers are, for example, dimethyl ether ((CH 3 ) 2 O), methyl ethyl ether (C 2 H 5 OCH 3 ) or diethyl ether ((C 2 H 5 ) 2 O).
- ketones mentioned above are, for example, acetone (( CH3 )2CO), methyl ethyl ketone ( C2H5COCH3 ) or diethylketone ( ( C2H5 ) 2CO ).
- aldehydes mentioned above are, for example, acetaldehyde (CH 3 CHO), propionaldehyde (C 2 H 5 CHO) or butanal (butyraldehyde) (C 3 H 7 CHO).
- the mixed substance separated by the separation device 2 is a mixed gas containing multiple types of gases.
- the separation device 2 of FIG. 10 includes a separation membrane composite 1, an outer cylinder 22, two sealing members 23, a supply section 26, a first recovery section 27, and a second recovery section 28. Separation membrane composite 1 and seal member 23 are accommodated in outer cylinder 22 .
- the supply portion 26 , the first recovery portion 27 and the second recovery portion 28 are arranged outside the outer cylinder 22 and connected to the outer cylinder 22 .
- outer cylinder 22 is not limited, it is, for example, a substantially cylindrical tubular member.
- Outer cylinder 22 is made of, for example, stainless steel or carbon steel.
- the longitudinal direction of the outer cylinder 22 is substantially parallel to the longitudinal direction of the separation membrane composite 1 .
- a supply port 221 is provided at one end in the longitudinal direction of the outer cylinder 22 (that is, the left end in the figure), and a first discharge port 222 is provided at the other end.
- a second discharge port 223 is provided on the side surface of the outer cylinder 22 .
- the supply portion 26 is connected to the supply port 221 .
- the first recovery section 27 is connected to the first discharge port 222 .
- the second recovery section 28 is connected to the second discharge port 223 .
- the internal space of the outer cylinder 22 is a closed space isolated from the space around the outer cylinder 22 .
- the two sealing members 23 are arranged along the entire circumference between the outer peripheral surface of the separation membrane composite 1 and the inner peripheral surface of the outer cylinder 22 in the vicinity of both ends in the longitudinal direction of the separation membrane composite 1 .
- Each seal member 23 is a substantially annular member made of a gas-impermeable material.
- the sealing member 23 is, for example, an O-ring made of flexible resin.
- the sealing member 23 is in close contact with the outer peripheral surface of the separation membrane composite 1 and the inner peripheral surface of the outer cylinder 22 over the entire circumference. Specifically, the sealing member 23 is in intimate contact with the dense portion 13 on the outer peripheral surface of the support 11 and indirectly in intimate contact with the outer peripheral surface of the support 11 via the dense portion 13 .
- Seals are provided between the sealing member 23 and the outer peripheral surface of the separation membrane composite 1 and between the sealing member 23 and the inner peripheral surface of the outer cylinder 22, so that almost or no gas can pass through. be.
- airtightness between the second discharge port 223 and the supply port 221 and the first discharge port 222 is ensured by the sealing member 23 .
- the supply unit 26 supplies the mixed gas to the internal space of the outer cylinder 22 through the supply port 221 .
- the supply unit 26 includes, for example, a blower or a pump that pumps the mixed gas toward the outer cylinder 22 .
- the blower or pump includes a pressure regulator that regulates the pressure of the mixed gas supplied to the outer cylinder 22 .
- the first recovery unit 27 and the second recovery unit 28 include, for example, a storage container that stores the gas drawn out from the outer cylinder 22, or a blower or pump that transfers the gas.
- the separation device 2 When the mixed gas is to be separated, the separation device 2 described above is provided. Subsequently, the supply unit 26 supplies a mixed gas containing a plurality of types of gases having different permeability to the zeolite membrane 12 into the inner space of the outer cylinder 22 .
- the main components of the mixed gas are CO2 and CH4 .
- the mixed gas may contain gases other than CO2 and CH4 .
- the pressure of the mixed gas supplied from the supply part 26 to the internal space of the outer cylinder 22 (that is, the introduction pressure) is, for example, 0.1 MPa to 20.0 MPa.
- the temperature at which the gas mixture is separated is, for example, 10°C to 150°C.
- the mixed gas supplied from the supply part 26 to the outer cylinder 22 is introduced into each through-hole 111 of the support 11 from the left end of the separation membrane composite 1 in the drawing, as indicated by an arrow 251 .
- a highly permeable gas for example, CO2 , hereinafter referred to as a “highly permeable substance” in the mixed gas passes through the zeolite membrane 12 provided on the inner peripheral surface of each through-hole 111, and It passes through the support 11 and is derived from the outer peripheral surface of the support 11 . This separates the highly permeable material from the less permeable gas (eg CH4, hereinafter referred to as "low permeable material”) in the gas mixture.
- the less permeable gas eg CH4, hereinafter referred to as "low permeable material
- the gas (hereinafter referred to as “permeating substance”) that permeates the separation membrane composite 1 and is led out from the outer peripheral surface of the support 11 passes through the second discharge port 223 as indicated by an arrow 253 . 2 is recovered by the recovery unit 28 .
- the pressure of the gas recovered by the second recovery section 28 via the second discharge port 223 (that is, permeation pressure) is, for example, approximately 1 atmosphere (0.101 MPa).
- the gas excluding the gas that has permeated the zeolite membrane 12 and the support 11 flows through each through-hole 111 of the support 11 from the left to the right in the figure. , and is recovered by first recovery section 27 via first discharge port 222 as indicated by arrow 252 .
- the pressure of the gas recovered by the first recovery section 27 via the first discharge port 222 is, for example, substantially the same as the introduction pressure.
- the impermeable substance may include a highly permeable substance that has not permeated the zeolite membrane 12, in addition to the low-permeable substance described above.
- the zeolite membrane 12 and the dense portion 13 may be provided on the outer peripheral surface of the monolithic support 11 in FIG. A membrane 12 and a dense portion 13 may be provided.
- the support may be a flat plate, and the dense portion 13 and the zeolite membrane 12 may be formed on one main surface of the support.
- the separation membrane composite 1 is manufactured as follows. First, on the main surface of the porous support, one position in a predetermined direction is set as a boundary position, and the slurry for dense portion formation is poured so as to cover the main surface from the boundary position toward one side in the predetermined direction. is applied.
- the viscosity of the dense portion-forming slurry is 2 dPa ⁇ s or more and 30 dPa ⁇ s or less.
- the slurry is dried in a state in which one end of the support in the predetermined direction is arranged on the lower side and the other end is arranged on the upper side, or The slurry is dried by blowing air along the main surface. Then, the dense portion 13 is formed by firing the slurry. The dense portion 13 covers the main surface from the boundary position toward one side in the predetermined direction on the main surface. Thereafter, a zeolite membrane 12 is formed on the main surface to cover the main surface from the boundary position toward the other side in the predetermined direction and to cover the dense portion 13 in the vicinity of the boundary position.
- each of the four measurement positions evenly set in the direction perpendicular to the predetermined direction on the main surface is measured along the predetermined direction and perpendicular to the main surface.
- the maximum value of the four evaluation angles at the four measurement positions is 5 degrees or more and 45 degrees or less.
- the predetermined direction corresponds to the longitudinal direction of the supports 11 and 11a in FIGS. 1 and 9. As shown in FIG.
- the separation membrane composite 1 may be produced by a method other than the production method described above.
- the closed porosity of the dense portion 13 may be greater than 10% within the attention range R1.
- the average roughness Za of the surface of the dense portion 13 within the range of interest R1 may be less than 0.01 ⁇ m or greater than 10 ⁇ m, and the surface roughness Ra of the dense portion 13 in the region where the zeolite membrane 12 does not exist is 0. It may be less than 0.01 ⁇ m or greater than 1 ⁇ m or less.
- the zeolite membrane 12 may contain SDA.
- Separation membrane composite 1 may further include a functional membrane or a protective membrane laminated on zeolite membrane 12 in addition to support 11 , dense portion 13 and zeolite membrane 12 .
- Such functional films and protective films may be inorganic films such as zeolite films, silica films or carbon films, or may be organic films such as polyimide films or silicone films.
- the functional film and the protective film laminated on the zeolite film 12 may be added with a substance that easily adsorbs specific molecules such as CO 2 .
- the separation membrane composite of the present invention can be used, for example, as a gas separation membrane, and can also be used in various fields as a separation membrane for gases other than gases, an adsorption membrane for various substances, and the like.
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Abstract
Description
[関連出願の参照]
本願は、2021年1月28日に出願された日本国特許出願JP2021-11640からの優先権の利益を主張し、当該出願の全ての開示は、本願に組み込まれる。
11,11a 支持体
12 ゼオライト膜
13 緻密部
P1 境界位置
R1 注目範囲
S11~S18 ステップ
θ 評価角度
Claims (7)
- 分離膜複合体であって、
多孔質の支持体と、
前記支持体の一の面上において、所定方向における一の位置を境界位置として、前記境界位置から前記所定方向の一方側に向かって前記面を覆う緻密部と、
前記支持体の前記面上において、前記境界位置から前記所定方向の他方側に向かって前記面を覆うとともに、前記境界位置の近傍において前記緻密部を覆う分離膜と、
を備え、
前記支持体の前記面上において前記所定方向に垂直な方向に均等に設定した4個の測定位置のそれぞれについて、前記所定方向に沿うとともに前記支持体の前記面に垂直な断面において、前記境界位置から前記所定方向の前記一方側に向かって30μmまでの注目範囲内にて、前記緻密部の前記分離膜側の表面上の各位置と前記境界位置とを結ぶ線と、前記支持体の前記面とがなす角度のうちの最大の角度を評価角度として取得する場合に、前記4個の測定位置における4個の評価角度の最大値が、5度以上かつ45度以下である。 - 請求項1に記載の分離膜複合体であって、
前記断面の前記注目範囲内において、前記緻密部における閉気孔率が10%以下である。 - 請求項1または2に記載の分離膜複合体であって、
前記分離膜の厚さが5μm以下であり、
前記断面の前記注目範囲内において、前記緻密部の前記分離膜側の表面に沿う直線を基準として算出される前記緻密部の前記表面の平均粗さが、0.01μm以上かつ10μm以下である。 - 請求項1ないし3のいずれか1つに記載の分離膜複合体であって、
前記分離膜の厚さが5μm以下であり、
前記分離膜の不存在領域における前記緻密部の表面粗さRaが、0.01μm以上かつ1μm以下である。 - 請求項1ないし4のいずれか1つに記載の分離膜複合体であって、
前記支持体の前記面が、前記所定方向に沿う円筒面であり、
前記4個の測定位置が、前記円筒面において周方向に90度間隔にて設定され、前記4個の測定位置における前記4個の評価角度の範囲の大きさが、15度以下である。 - 請求項1ないし5のいずれか1つに記載の分離膜複合体であって、
前記支持体の前記面が、前記所定方向に沿う円筒面であり、
前記境界位置が、前記所定方向の前記一方側における前記支持体の端部に設けられ、前記緻密部が前記支持体の前記一方側の端面も覆う。 - 分離膜複合体の製造方法であって、
a)多孔質の支持体の一の面上において、所定方向における一の位置を境界位置として、前記境界位置から前記所定方向の一方側に向かって前記面を覆うように緻密部形成用のスラリーを塗布する工程と、
b)前記所定方向における前記支持体の前記一方側の端部を下側に配置し、他方側の端部を上側に配置した状態で前記スラリーを乾燥させる、または、前記支持体の前記他方側から前記一方側に向かって前記面に沿って送風を行うことにより、前記スラリーを乾燥させる工程と、
c)前記スラリーを焼成することにより、緻密部を形成する工程と、
d)前記支持体の前記面上において、前記境界位置から前記所定方向の前記他方側に向かって前記面を覆うとともに、前記境界位置の近傍において前記緻密部を覆う分離膜を形成する工程と、
を備え、
前記a)工程における前記スラリーの粘度が、2dPa・s以上かつ30dPa・s以下である。
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DE112021006959.4T DE112021006959T5 (de) | 2021-01-28 | 2021-11-10 | Trennmembrankomplex und Verfahren zur Herstellung eines Trennmembrankomplexes |
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