WO2013125506A1 - 分離膜エレメント及び分離膜モジュール - Google Patents
分離膜エレメント及び分離膜モジュール Download PDFInfo
- Publication number
- WO2013125506A1 WO2013125506A1 PCT/JP2013/053936 JP2013053936W WO2013125506A1 WO 2013125506 A1 WO2013125506 A1 WO 2013125506A1 JP 2013053936 W JP2013053936 W JP 2013053936W WO 2013125506 A1 WO2013125506 A1 WO 2013125506A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- separation membrane
- resin
- separation
- membrane element
- water
- Prior art date
Links
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Images
Classifications
-
- 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
- B01D69/06—Flat membranes
- B01D69/061—Membrane bags or membrane cushions
-
- 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
- B01D63/08—Flat membrane modules
- B01D63/082—Flat membrane modules comprising a stack of flat membranes
-
- 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
- B01D63/08—Flat membrane modules
- B01D63/082—Flat membrane modules comprising a stack of flat membranes
- B01D63/084—Flat membrane modules comprising a stack of flat membranes at least one flow duct intersecting the membranes
-
- 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
- B01D69/10—Supported membranes; Membrane supports
-
- 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
- B01D69/10—Supported membranes; Membrane supports
- B01D69/107—Organic support material
-
- 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
- B01D69/1213—Laminated layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
- B32B37/1284—Application of adhesive
- B32B37/1292—Application of adhesive selectively, e.g. in stripes, in patterns
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2311/00—Details relating to membrane separation process operations and control
- B01D2311/26—Further operations combined with membrane separation processes
- B01D2311/2661—Addition of gas
- B01D2311/2665—Aeration other than for cleaning purposes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2313/00—Details relating to membrane modules or apparatus
- B01D2313/14—Specific spacers
- B01D2313/146—Specific spacers on the permeate side
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2315/00—Details relating to the membrane module operation
- B01D2315/06—Submerged-type; Immersion type
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2319/00—Membrane assemblies within one housing
- B01D2319/04—Elements in parallel
Definitions
- the present invention relates to a separation membrane element and a separation membrane module suitable for water treatment fields such as drinking water production, water purification treatment, waste water treatment, and food industry.
- the membrane separation activated sludge method is a treatment method in which a separation membrane is immersed in an activated sludge tank and the activated sludge and treated water are separated by a membrane. Since MBR is space-saving and provides good water quality, the introduction of MBR has been promoted mainly in small facilities in Japan, and in large facilities exceeding 100,000 m 3 / day in many new facilities overseas.
- Patent Document 1 provides a membrane (separation membrane) that covers the surface of a membrane support plate as a membrane element to be used by being placed in a casing at appropriate intervals and immersed in a liquid to be treated. And forming a permeate channel that communicates with the permeate suction tube.
- a membrane separation membrane
- many flat membrane type elements are configured by attaching a separation membrane to a membrane support plate, and a groove for collecting membrane permeate is formed on the membrane support plate. Ingenuity has been made.
- the membrane support plate has a problem that it is thick and heavy.
- Patent Document 2 proposes a bag-like flat membrane element in which the peripheral edge surfaces of two flat membranes are sealed with a resin adhesive.
- Patent Document 3 discloses a filter including a first filtration membrane, a first adhesive net made of a thermoplastic polymer, a drainage woven fabric, a second adhesive net of a thermoplastic polymer, and a second filtration membrane. Composite materials are described. The first and second filtration membranes are bonded to the drainage woven fabric by the first and second adhesive nets.
- a resin such as ABS is usually used for the support plate.
- aeration is performed from the lower part of the membrane element immersed in the liquid to be treated, and the membrane surface is always washed to obtain treated water from activated sludge having a high solid content concentration. It is possible. In such a use environment, since the membrane element receives energy from aeration, the membrane element is required to have a rigidity that does not lose the energy of the aeration.
- the thickness of the support plate is required to be at least about 4 mm, which has been a factor in increasing the cost of the membrane element and membrane module.
- the support plate is thick, there is a problem that when a plurality of membrane elements are arranged in parallel to form a membrane module, the membrane area (filling rate of the separation membrane) per installation area becomes low.
- Patent Document 2 the permeation side surfaces of the separation membrane facing each other at the time of filtration are in contact with each other, the flow resistance is increased, and a sufficient amount of permeated water cannot be obtained. There was a problem that the membrane element did not have a certain degree of strength.
- the membrane element receives energy from aeration in the MBR usage environment
- the membrane element and the membrane module have the flexibility to allow the energy of the aeration to escape as well as the membrane, and reduce the cost as much as possible.
- a module is required, such a membrane element and a membrane module have not been obtained yet.
- the present invention aims to solve the above-mentioned problems of the prior art and provide a technique capable of improving the amount of permeated water.
- the separation membrane element and the separation membrane module of the present invention that achieve the above object are characterized by having the following configuration.
- a separation membrane pair having two separation membranes arranged so that the surfaces on the permeate side face each other, and two or more resin parts that adhere to both the surfaces on the permeate side that face each other.
- a separation membrane element wherein a peripheral edge of the separation membrane pair is sealed.
- a separation membrane element according to any one of the above. (9) A separation membrane module in which a plurality of separation membrane elements according to any one of (1) to (8) are arranged in parallel so that the water collecting portions of adjacent separation membrane elements are not located at the same position. Separation membrane module characterized by being arranged.
- FIGS. 1A and 1B are cross-sectional views schematically showing an example of an embodiment of a separation membrane element of the present invention.
- FIG. 1A is parallel to the membrane surface at the thickness center of the separation membrane element.
- FIG. 1B is a cross-sectional view when the separation membrane element is cut in the thickness direction.
- FIG. 2 is a cross-sectional view schematically showing an example of an embodiment of the separation membrane element of the present invention, and is a cross-sectional view corresponding to FIG.
- FIG. 3 is a cross-sectional view schematically showing an example of the embodiment of the separation membrane element of the present invention, and is a cross-sectional view corresponding to FIG.
- FIGS. 4 (a) and 4 (b) are cross-sectional views schematically showing an example of the embodiment of the separation membrane element of the present invention, and are cross-sectional views corresponding to FIGS. 1 (a) and 1 (b).
- FIG. 5 is a cross-sectional view schematically showing an example of an embodiment of the separation membrane element of the present invention, and is a cross-sectional view corresponding to FIG.
- FIG. 6 is a cross-sectional view schematically showing an example of the embodiment of the separation membrane element of the present invention, and is a cross-sectional view corresponding to FIG.
- FIG. 7 is a cross-sectional view schematically showing an example of the embodiment of the separation membrane element of the present invention, and is a cross-sectional view corresponding to FIG. FIG.
- FIGS. 2 to 3, 4 (a), and 5 to 7 are sectional views in plan view of other embodiments of the separation membrane element, and FIG. 4 (b) is another embodiment of the separation membrane element. It is sectional drawing of the thickness direction.
- reference numeral 1 denotes a separation membrane element
- reference numeral 2 denotes a separation membrane
- reference numeral 3 denotes a separation functional layer
- reference numeral 4 denotes a base material
- reference numeral 5 denotes a gap between the separation membranes
- reference numeral 6 Is a sealing part formed by a peripheral resin layer
- numeral 7 is an inner resin part
- numeral 8 is a water collecting part
- numeral 9 is a water collecting port.
- the separation membrane element 1 of the present invention is composed of a pair of two separation membranes 2 and 2, and the separation membranes 2 and 2 are arranged so that the permeation sides face each other and a predetermined gap 5 is opened.
- the separation membrane element may be simply referred to as “element”.
- the periphery of the gap 5 is sealed with resin to form a sealing portion 6.
- a part between the separation membranes 2 and 2 inside the peripheral sealing portion 6 is connected by two or more inner resin portions 7.
- the separation membrane forming the pair may be two separable separation membranes, or may be a folded separation membrane. A gap is provided between the permeation side surfaces of the opposing separation membrane.
- the sealing part 6 is arrange
- the sealing part 6 seals the gap between the separation membranes in the separation membrane pair by adhering to both of the two permeable side surfaces facing each other in the separation membrane pair.
- a bag-like film is formed. Sealing means that the supply water does not flow directly into the bag-like membrane by adhesion, pressure bonding, welding, fusion, folding, etc. (that is, the supply water does not flow through the separation membrane and does not flow).
- the permeated water that has passed through the separation membrane does not leak outside the separation membrane element except for the water collecting portion 8.
- the configuration in which “the separation membranes are connected” by the resin portion 7 means that one resin portion 7 permeates the permeation side surface of one separation membrane 2 and the other separation membrane 2 opposed thereto in one separation membrane pair. Refers to a configuration that adheres to both sides. That is, in the separation membrane pair, one separation membrane is fixed to the other separation membrane via a resin.
- inside refers to the surface of the permeation side surface of the separation membrane excluding the peripheral edge.
- the portion surrounded by the sealing portion corresponds to “inside”.
- FIG. 1 illustrates a form in which the separation membrane 2 is formed by laminating the separation functional layer 3 on the substrate 4, and the surface of the substrate 4 opposite to the separation functional layer 3 is permeated by the separation membrane 2. Become side.
- the configuration of the separation membrane 2 is not limited to the illustrated example.
- the separation membrane is not limited as long as it separates components in the fluid supplied to the surface of the separation membrane and obtains a permeated fluid that has permeated the separation membrane.
- a separation membrane a separation functional layer, a porous support layer, and a base material can be provided, for example.
- each resin part 7 can have a comparatively high rigidity, the freedom degree in structures, such as the number of the resin parts 7 per unit area of a separation membrane, and the area of the resin part 7, is comparatively high.
- the resin component of the resin part 7 may be impregnated in the base material of the separation membrane.
- resin When resin is disposed on the base material on the permeation side of the separation membrane and heated from the surface of the separation functional layer of the separation membrane, the impregnation of the resin proceeds from the permeation side of the separation membrane toward the functional layer surface.
- the adhesion between the resin and the substrate becomes stronger. For this reason, when the manufactured element is washed, even if it is washed from the permeation side with a chemical solution, the separation membrane pair is hardly separated.
- the separation membrane element of the present invention secures a gap between the separation membranes and reduces the flow resistance of the permeated water without arranging such a member such as a spacer.
- the gap 5 on the permeation side of the separation membrane is preferably in the range of 50 ⁇ m to 5000 ⁇ m.
- the gap between the separation membranes exceeds 5000 ⁇ m, bubbles may violently collide with the membrane surface and be damaged by an aeration operation during water treatment operation.
- the gap between the separation membranes is less than 50 ⁇ m, the inner space on the permeate side is narrow and the flow resistance of the permeate increases, and the amount of permeate decreases. Therefore, according to the configuration of the present invention, the flow path of the permeated liquid can be secured stably, and the permeation side can be cleaned with the chemical liquid.
- the gap between the separation membranes is more preferably in the range of 500 ⁇ m or more and 3000 ⁇ m or less.
- a flow path can be secured by sandwiching a flow path material such as a net inside the transmission side.
- a flow path material such as a net inside the transmission side.
- the efficiency of securing the flow path with respect to the entire thickness of the separation membrane element is poor.
- the pressure formed on the separation membrane from the permeation side may cause the bag formed of the separation membrane to swell and damage the separation membrane.
- the separation membrane may be peeled off by washing from the permeation side with a chemical solution. If it is large, the flow path is blocked by the resin and the amount of water in the permeate decreases. To do. Therefore, it is preferable that the area ratio of the inner resin portion 7 is in a range of 1% to 70% with respect to the inner area of the separation membrane 2. More preferably, it is the range of 10% or more and 50% or less.
- the planar shape of the resin part 7 in the present invention that is, the shape of the resin part 7 projected onto the separation membrane.
- An important point of the present invention is that the resin is applied to the separation membrane 2 to form the resin portion 7 so that the resin has an effect of an adhesive interlining, and the separation membrane 2 and the separation membrane element have appropriate flexibility and rigidity. Is to give.
- the shape when the resin portion 7 is observed from the upper part of the film surface is not particularly limited as long as the desired effect as an element is not impaired.
- the cross-sectional shape of the inner resin portion 7 is an elliptical dot shape.
- the cross-sectional shape in plan view of the inner resin portion 7 is not limited to this example, and is formed in a dot shape such as a circle, a polygon, or an indeterminate shape, or a linear shape such as a straight line, a curve, a wavy line, a zigzag, or a lattice. can do.
- the arrangement of the dot-shaped resin is not particularly limited, such as a lattice shape or a staggered shape.
- the resin part in the separation membrane element shown in FIG. 2 is an example in which linear resin parts 7 arranged in parallel in a broken line shape in the vertical direction are formed.
- the resin part in the separation membrane element shown in FIG. 3 is an example in which linear resin parts 7 arranged in parallel in a broken line shape inclined at an angle ⁇ are formed.
- the resin part in the separation membrane element shown in FIGS. 4A and 4B is a striped pattern of a striped steel plate composed of a long linear resin part 7 facing in the vertical direction and a short linear resin part 7 facing in the horizontal direction. This is an example in which the resin 7 having the form is formed.
- the resin part in the separation membrane element shown in FIG. 5 has a form in which the length of each resin part 7 is substantially the same and the extending direction of the resin part 7 is inclined by about 45 ° with respect to the peripheral sealing part 6. It is the example made into the striped pattern of a striped steel plate.
- the resin part in the separation membrane element shown in FIG. 6 is a striped steel plate having a form in which three linear resin parts 7 facing up and down and three linear resin parts 7 facing left and right are combined. This is an example of a striped pattern.
- the resin part in the separation membrane element shown in FIG. 6 is an example in which substantially circular resin parts 7 are arranged in an orderly manner in the vertical and horizontal directions.
- the element By adjusting the shape of the resin part 7 on the inner side, the element can be designed so as to satisfy the required separation characteristics and permeation performance conditions.
- the projection image of the resin part 7 onto the separation membrane is discontinuous. That is, two or more resin parts are arranged on one separation membrane at intervals in the planar direction of the separation membrane. More specifically, it is preferable that 1 or more, 5 or more, or 10 or more resin portions are provided per 5 cm square in the inner part of the permeation side surface of the separation membrane. Moreover, it is preferable that 100 or less, 50 or less, or 30 or less resin parts are provided per 5 cm square.
- the shape of the resin portion 7 is a striped plate because the rigidity and durability of the separation membrane element can be improved.
- Striped plate shape indicates a striped pattern of hot-rolled striped steel plate that is generally used for flooring materials.
- the striped pattern of the striped steel plate has various shapes such as the number, length, and angle of the stripes, and the pitch of adjacent stripes.
- the greatest feature of the striped steel strip is that the striped pattern does not have a series of directions (anisotropy). That is, as illustrated in FIG. 4A, a striped pattern in which the adjacent stripes are arranged in alternate directions (horizontal and vertical directions).
- a floor surface having a striped steel plate on its surface can obtain an equivalent anti-slip effect in any direction.
- the bonding line has no directionality, and the rigidity of the membrane element is reduced. It can be further increased.
- the “adhesion line” starts from an arbitrary resin portion 7-1 adjacent to the sealing portion 6 on the periphery of the element, such as the resin portion 7 arranged in a broken line shape shown in FIGS.
- the resin portion 7-2 adjacent to the sealing portion 6 on the periphery of another element facing or adjacent to this starting point is set as the end point, the end point is reached from the starting point at any angle ⁇ , and from the starting point to the end point.
- “Align” means that when the resin part existing between the start point and the end point has directionality, the extending direction of all the resin parts between the start point and the end point is parallel to the straight line from the start point to the end point. That means.
- the shape of the resin part is a stripe pattern of a striped steel plate, it does not have an adhesive line, and the resin part array has no directionality (that is, isotropic). For this reason, since the bending can be suppressed particularly in the wastewater treatment application in which aeration is performed, it is preferable that the shape of the resin portion is a striped pattern of the striped steel plate.
- the striped pattern of the striped steel plate includes, for example, a group of short ridges A arranged in one direction and a group of short ridges B arranged in a direction orthogonal to the direction of the ridges A.
- a stripe pattern in which the stripes B are alternately arranged can be exemplified.
- the protrusions A and protrusions B can be arranged in substantially parallel and substantially perpendicular directions with respect to the sealing portion 6 at the periphery of the separation membrane.
- the extension direction of the protrusion A and the protrusion B can also be made to incline with respect to the sealing part 6 of the periphery of a separation membrane.
- FIG. 5 the example of FIG.
- the ridges A and the ridges B may be alternately arranged one above the other as shown in FIG. 4, or a plurality of ridges A and a plurality of ridges B as shown in FIG. May be alternately arranged vertically and horizontally.
- the period and arrangement regularity are not particularly limited with respect to the vertical and horizontal directions and the direction and angle of each adjacent stripe.
- the direction of the stripes may be arbitrary, such as parallel or perpendicular to the film periphery, or 45 °, but is preferably substantially parallel and substantially perpendicular to the film periphery from the viewpoint of manufacturability. .
- the length, number, and pitch interval of the stripes are not particularly limited as long as the characteristics of giving appropriate flexibility and rigidity to the separation membrane 2 and the separation membrane element are satisfied.
- polyolefin such as ethylene vinyl acetate copolymer, polyethylene, a polypropylene, an olefin copolymer, etc.
- polymers such as urethane resin and epoxy resin can also be selected.
- a thermoplastic polymer is easy to mold, the shape of the resin can be made uniform.
- JIS K-2531 JIS K-2207 / 2425, JIS K6863-1994, and ASTM D-36 are preferably used.
- the softening point measured by any one method may be included in the above-described range. More preferably, the softening point measured by the method of JIS K6863-1994 may be included in the above range.
- the method of adhering the resin to the perimeter and part of the inner side of the separation membrane is not particularly limited, but the required separation characteristics and permeation performance conditions can be satisfied by changing the processing temperature and the type of resin selected.
- the shape of the resin can be adjusted freely as possible.
- the separation membrane is a flat membrane-like separation membrane, and preferably has a separation functional layer formed on a non-woven base material.
- the separation functional layer is preferably composed of a crosslinked polymer in terms of pore diameter control and durability. From the viewpoint of the separation performance of the components to be separated, a separation functional layer obtained by polycondensation of a polyfunctional amine and a polyfunctional acid halide on a porous support layer, an organic-inorganic hybrid functional layer, and the like are preferable.
- a porous support layer such as a cellulose membrane, a polyvinylidene fluoride membrane, a polyethersulfone membrane, or a polysulfone membrane, which has both a separation function and a support function, can also be used. That is, the separation functional layer and the porous support layer may be realized as a single layer.
- the separation membrane constituting the separation membrane element of the present invention is preferably composed of a base material and a separation functional layer, and in particular, a separation membrane formed with a separation functional layer made of a polyvinylidene fluoride resin may be used.
- a layer in which the resin constituting the separation functional layer and the base material are mixed is interposed between the base material and the separation functional layer.
- the separation functional layer may be present on one side with respect to the base material, or may be present on both sides.
- the separation functional layer may have a symmetric structure or an asymmetric structure with respect to the base material. Further, when the separation functional layer is present on both sides with respect to the substrate, the separation functional layers on both sides may be continuous through the substrate or may be discontinuous. .
- the base material has a function of supporting the separation functional layer and giving strength to the separation membrane.
- the material constituting the base material is not particularly limited, such as an organic base material or an inorganic base material, but an organic base material is preferable from the viewpoint of easy weight reduction.
- the organic substrate include woven and knitted fabrics and nonwoven fabrics made of organic fibers such as cellulose fibers, cellulose triacetate fibers, polyester fibers, polypropylene fibers, and polyethylene fibers. Among these, a nonwoven fabric whose density is relatively easy to control is particularly preferable.
- This separation membrane forms a separation functional layer by adhering a film-forming stock solution containing a polyvinylidene fluoride resin and a pore-opening agent to one or both surfaces of a substrate and coagulating it in a coagulating liquid containing a non-solvent.
- the means for attaching the film-forming stock solution to the surface of the substrate may be application of the film-forming stock solution, or the substrate may be immersed in the film-forming stock solution.
- the film-forming stock solution to the substrate it may be applied on one side of the substrate or on both sides. It is also possible to join both layers after forming only the separation functional layer separately from the substrate.
- the membrane-forming solution film for forming the separation functional layer on the base material may be brought into contact with the coagulating solution, or the film-forming stock solution film for forming the separation function layer may be used as the base material. The whole may be immersed in the coagulation liquid.
- a method of bringing the membrane-forming solution film formed on the base material into contact with the coagulation bath surface A substrate is brought into contact with a smooth plate such as a glass plate or a metal plate and attached so that the coagulation bath does not wrap around the substrate, and the substrate having the film-forming solution film is immersed in the coagulation bath together with the plate.
- the base material may be attached to the plate and then the film of the film forming stock solution may be formed, or the film of the film forming raw solution may be formed on the base material and then attached to the plate.
- the pore-opening agent may be any one that can be extracted by the coagulation liquid, and is preferably highly soluble in the coagulation liquid.
- inorganic salts such as calcium chloride and calcium carbonate can be used.
- polyoxyalkylenes such as polyethylene glycol and polypropylene glycol
- water-soluble polymers such as polyvinyl alcohol, polyvinyl butyral, and poracrylic acid, and glycerin can also be used.
- the pore-opening agent can be arbitrarily selected depending on the type of resin used in the film-forming stock solution.
- a polymer having polyethylene glycol as a main component is preferable.
- the polyoxyalkylene structure includes — (CH 2 CH 2 O) n —, — (CH 2 CH 2 (CH 3 ) O) n —, — (CH 2 CH 2 CH 2 O) n —, — (CH 2 CH 2 CH 2 CH 2 O) n — and the like can be mentioned, but — (CH 2 CH 2 O) n —so-called polyoxyethylene is particularly preferred from the viewpoint of hydrophilicity.
- fatty acid ester structure examples include fatty acids having a long-chain aliphatic group.
- the long-chain aliphatic group may be linear or branched, and examples of the fatty acid include stearic acid, oleic acid, lauric acid, and palmitic acid.
- fatty acid ester derived from fats and oils such as beef tallow, palm oil, coconut oil, etc. are also mentioned.
- surfactant having a hydroxyl group examples include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, glycerin, sorbitol, glucose, and sucrose.
- the surfactant used as a pore opening agent in the present invention preferably contains two or more of a polyoxyalkylene structure, a fatty acid ester structure and a hydroxyl group.
- polyoxyethylene sorbitan fatty acid ester includes polyoxyethylene sorbitan monostearate, polyoxyethylene palm Oil fatty acid sorbitan, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene fatty acid ester, polyethylene glycol monostearate, polyethylene glycol monooleate, polyethylene glycol monolaurate Can be mentioned.
- These surfactants are particularly preferable because they not only improve the dispersibility of the inorganic fine particles, but also have the characteristics that even if they remain in the porous layer and are dried, the water permeability and blocking properties are not lowered. Further, these surfactants can be used by applying to the separation membrane after the separation membrane is produced and drying it, and can prevent deterioration of water permeability and inhibition.
- NMP N-methylpyrrolidone
- DMAc Dimethylacetamide
- DMF N-dimethylformamide
- DMSO dimethylsulfoxide
- acetone methyl ethyl ketone
- NMP, DMAc, DMF, and DMSO which are highly soluble in polyvinylidene fluoride resins, can be preferably used.
- a non-solvent can be added to the film forming stock solution.
- the non-solvent does not dissolve the polyvinylidene fluoride resin or other organic resins, and acts to control the size of the pores by controlling the solidification rate of the polyvinylidene fluoride resin and other organic resins.
- water and alcohols such as methanol and ethanol can be used. Of these, water and methanol are preferred from the viewpoint of ease of wastewater treatment and price. These may be mixed.
- the polyvinylidene fluoride resin is 5% to 30% by weight, the pore-opening agent is 0.1% to 15% by weight, the solvent is 45% to 94.8% by weight, and the non-solvent is It is preferably in the range of 0.1% to 10% by weight.
- the range of 8 wt% to 20 wt% is more preferable.
- the amount of the pore-opening agent is too small, the water permeability may decrease, and if the amount is too large, the strength of the porous layer may decrease. In addition, if it is extremely large, it may remain excessively in the polyvinylidene fluoride resin and elute during use, and the quality of the permeated water may deteriorate or the water permeability may change. Therefore, a more preferable range is 0.5 to 10% by weight. Further, when the amount of the solvent is too small, the stock solution is easily gelled, and when the amount is too large, the strength of the porous layer is lowered.
- the solvent is more preferably in the range of 60% to 90% by weight.
- the non-solvent is more preferably 0.5% by weight to 5% by weight.
- the coagulation bath a non-solvent or a mixed solution containing a non-solvent and a solvent can be used.
- the non-solvent in the coagulation bath is preferably at least 80% by weight of the coagulation bath. If the amount is too small, the coagulation rate of the polyvinylidene fluoride resin becomes slow, and the pore diameter becomes large.
- the non-solvent in the coagulation bath is more preferably in the range of 85% to 100% by weight.
- the non-solvent content in the coagulation bath is preferably at most 40% by weight.
- the content of the non-solvent is more preferably in the range of 1% by weight to 40% by weight.
- the pore size on the surface of the porous layer and the size of the macrovoids can be controlled. If the temperature of the coagulation bath is too high, the coagulation rate will be too fast. Conversely, if the temperature is too low, the coagulation rate will be too slow, so it is usually selected within the range of 15 ° C to 80 ° C. preferable. More preferably, it is in the range of 20 ° C to 60 ° C.
- the separation membrane element of the present invention can be applied to any of reverse osmosis membranes, nanofiltration membranes, ultrafiltration membranes, and microfiltration membranes. Further, one or more appropriate membranes may be selected and combined depending on the size of the separation symmetric substance, but ultrafiltration membranes and microfiltration membranes are particularly preferred for treating sewage wastewater.
- the water collection port 9 is disposed in the separation membrane element, so that the permeated water filtered by the separation membrane flows through the space between the resin parts 7 and passes through the water collection port 9. Thus, it can be taken out of the separation membrane element.
- the water collecting portion 8 constituting the separation membrane element 1 may be at the end portion or inside of the element as long as the desired effect is not impaired, and is not particularly limited.
- a water collection portion 8 is provided at the end of the separation membrane element and is attached to a fixing jig 23 that supports the water collection port 9. Is preferred.
- FIG. 7 shows the separation membrane element 1 and the water collecting port 9 of another form side by side. Moreover, in FIG. 9, the top view (a) and front view (b) of this water collection port 9 are shown.
- the water collection port 9 is composed of upper and lower hollow members.
- the lower part of the water collection port 9 is arranged so that the two curved surfaces are hollow, the lower part is opened, the upper part is closed with a substantially flat surface, and an opening is provided at the approximate center of the upper flat surface.
- An elliptical cylinder (upper hollow member) is connected.
- a sealing method a method by heat welding, a method using an adhesive, and the like can be considered, but the sealing method is not particularly limited. In order to make sealing more reliable, a method in which heat welding and an adhesive are used in combination is also conceivable.
- the shape of the attachment portion is not particularly limited, but an appropriate one may be selected from the size of the separation membrane element 1 and the size and shape of the water collecting port 9.
- the separation membrane element of the present invention is an element without a support plate, the thickness of the entire element can be reduced, and the membrane area per unit area (separation membrane filling rate) can be increased as a membrane module. Is possible.
- a water collection port 9 is attached to the separation membrane element 1. For this reason, the problem is how to arrange the water collection port rather than the membrane portion to increase the filling rate of the separation membrane element 1. Therefore, the separation membrane module of the present invention is characterized in that it is arranged so that the water collecting ports of adjacent elements do not interfere with each other.
- FIG. 10C shows a schematic view of the separation membrane module 10 in which a plurality of separation membrane elements 1a and 1b are alternately arranged as viewed from above.
- FIGS. 10A to 10C show an example, and the structure is not limited to this structure as long as the adjacent water collection ports 9 can be arranged so as not to interfere with each other.
- the separation membrane elements 1a and 1b described in FIGS. 10 (a) and 10 (b) take one corner of a rectangular flat membrane-like separation membrane, have a shape having an inclined side 11, and a water collecting portion on the inclined side.
- the water collecting port 9 is arranged.
- the water collecting pipe is arranged on the side of the membrane element.
- this membrane element can be used as a membrane module having a structure in which a plurality of membrane elements are accommodated in a housing.
- the membrane module has a structure in which a plurality of membrane elements are fixed in a state of being arranged in parallel.
- This membrane module is immersed in a tank in which a liquid to be treated such as waste water is stored, and can be used for membrane filtration.
- These membrane elements and membrane modules are provided with a liquid collecting means for collecting the permeated liquid that has passed through the separation membrane, and can be used as a liquid treatment apparatus for the treatment of sewage wastewater.
- the membrane module 12 is configured such that a plurality of membrane elements 13 are accommodated in a housing so that a space is formed between the membrane surfaces of adjacent membrane elements 13 in parallel with each other.
- This membrane module is used so as to be immersed in water to be treated such as organic waste water stored in the membrane immersion water tank 14.
- a plurality of membrane elements 13 loaded in the vertical direction are provided inside the membrane module 12, and an air diffuser 15 is provided therebelow.
- the air diffuser 15 supplies the gas from the blower 16 to the membrane surface of the separation membrane.
- a pump 17 that sucks the permeated water 20 is provided on the downstream side of the membrane module 12.
- the liquid to be treated such as wastewater passes through the separation membrane of the membrane element 13 by the suction force of the pump 17.
- suspended substances such as microbial particles and inorganic particles contained in the liquid to be treated are filtered.
- the permeated water that has passed through the separation membrane flows out to the permeate side of the separation membrane, passes through a water collection port arranged at the end of the element, and is taken out through the pump 17 to the outside of the water tank to be treated.
- the air diffuser 15 in parallel with the filtration, the air diffuser 15 generates bubbles, and the upward flow parallel to the membrane surface of the membrane element generated by the air lift action of the bubbles separates the filtrate deposited on the membrane surface.
- the liquid to be treated is not limited to sewage wastewater, but can be used for water purification, clean water treatment, wastewater treatment, industrial water production, etc. in the water treatment field.
- sewage, drainage, etc. can be treated water.
- PVDF Polyvinylidene fluoride
- PEG 20,000 weight average molecular weight 280,000
- N, N-dimethylformamide (DMF) was used as a solvent
- H 2 O was used as a non-solvent.
- non-woven fabric made of rectangular polyester fiber having a density of 0.42 g / cm 3 and a size of 50 cm width ⁇ 150 cm length as a base material
- it was applied to the base material, and after coating, Immediately, it was immersed in pure water at 20 ° C. for 5 minutes and further immersed in hot water at 90 ° C. for 2 minutes to wash away N, N-dimethylformamide as a solvent and polyethylene glycol as a pore-opening agent.
- a resin was applied to the inner region so as to be a dot shape having a length of 4 mm, a width of 3 mm, a vertical interval of 8 mm, a horizontal interval of 4 mm, and a height of about 1 mm.
- the gap on the permeate side of the separation membrane element thus obtained was 0.5 mm (500 ⁇ m).
- the inner resin portion was a substantially elliptical dot shape having a major axis of 8.0 mm, a minor axis of 4.5 mm, a vertical interval of 4.0 mm, and a horizontal interval of 2.5 mm, and the area ratio was 35% (see FIG. 1).
- the cross-sectional shape of the inner resin part was substantially rectangular.
- Example 2 As in Example 1, except that the height at which the ethylene vinyl acetate copolymer resin was applied and the thickness of the aluminum plate as the spacer were changed so that the gap on the permeate side of the separation membrane was 0.05 mm (50 ⁇ m).
- the inner resin portion was a substantially elliptical dot shape having a major axis of 8.0 mm, a minor axis of 4.5 mm, a vertical interval of 4.0 mm, and a horizontal interval of 2.5 mm, and the area ratio was 35 % (See FIG. 1).
- the cross-sectional shape of the inner resin part was substantially rectangular.
- the water permeability of the separation membrane was 24.6 ⁇ 10 ⁇ 9 m 3 / m 2 / s / Pa, which was a lower value than Example 1.
- Table 1 shows the results of the area ratio of the resin part, the gap on the permeate side, and the water permeation performance.
- Example 3 The separation membrane was the same as in Example 1 except that the height at which the ethylene vinyl acetate copolymer resin was applied and the thickness of the aluminum plate as the spacer were changed so that the gap on the permeate side of the separation membrane was 2 mm (2000 ⁇ m).
- the inner resin portion was a substantially elliptical dot shape having a major axis of 8.0 mm, a minor axis of 4.5 mm, a vertical interval of 4.0 mm, and a horizontal interval of 2.5 mm, and the area ratio was 35 % (See FIG. 1). Further, the cross-sectional shape of the inner resin portion was substantially rectangular.
- the water permeability of the separation membrane was 25.8 ⁇ 10 ⁇ 9 m 3 / m 2 / s / Pa, which was almost the same value as in Example 1.
- Table 1 shows the results of the area ratio of the resin part, the gap on the permeate side, and the water permeation performance.
- Example 4 The separation membrane was the same as in Example 1 except that the height at which the ethylene vinyl acetate copolymer resin was applied and the thickness of the aluminum plate as the spacer were changed so that the gap on the permeate side of the separation membrane was 5 mm (5000 ⁇ m).
- the inner resin portion was a substantially elliptical dot shape having a major axis of 8.0 mm, a minor axis of 4.5 mm, a vertical interval of 4.0 mm, and a horizontal interval of 2.5 mm, and the area ratio was 35 % (See FIG. 1). Further, the cross-sectional shape of the inner resin portion was substantially rectangular.
- the water permeability of the separation membrane was 25.5 ⁇ 10 ⁇ 9 m 3 / m 2 / s / Pa, which was almost the same value as in Example 1.
- Table 1 shows the results of the area ratio of the resin part, the gap on the permeate side, and the water permeation performance.
- Example 5 A separation membrane element was prepared in the same manner as in Example 1 except that the size of the dot shape and the vertical and horizontal intervals to which the ethylene vinyl acetate copolymer resin was applied were changed so that the area ratio of the inner resin portion was 1%.
- the inner resin portion was a substantially circular dot shape having a major axis of 1.1 mm, a minor axis of 1.1 mm, a vertical interval of 9.4 mm, and a horizontal interval of 8.3 mm.
- the cross-sectional shape of the inner resin part was substantially elliptical.
- the water permeability of the separation membrane was 24.7 ⁇ 10 ⁇ 9 m 3 / m 2 / s / Pa, which was almost the same value as in Example 1.
- Table 1 shows the results of the area ratio of the resin part, the gap on the permeate side, and the water permeation performance.
- Example 6 The size of the dot shape to apply the ethylene vinyl acetate copolymer resin and the vertical and horizontal spacing, and the spacer so that the gap on the permeate side of the separation membrane is 2 mm (2000 ⁇ m) and the area ratio of the inner resin part is 5%
- a separation membrane element was produced and evaluated in the same manner as in Example 3 except that the thickness of a certain aluminum plate was changed.
- the inner resin part was an abbreviation having a major axis of 2.6 mm, a minor axis of 1.8 mm, and a vertical and horizontal interval of 7.5 mm. It was an elliptical dot shape. Moreover, the cross-sectional shape of the inner resin part was substantially elliptical.
- the cross-sectional shape of the inner resin portion was substantially rectangular.
- the water permeability of the separation membrane was 25.1 ⁇ 10 ⁇ 9 m 3 / m 2 / s / Pa, which was almost the same value as in Example 3.
- Table 1 shows the results of the area ratio of the resin part, the gap on the permeate side, and the water permeation performance.
- Example 7 Other than changing the size and vertical / horizontal spacing of the ethylene vinyl acetate copolymer resin so that the gap on the permeate side of the separation membrane is 2 mm (2000 ⁇ m), and the area ratio of the inner resin part is 20%
- the separation membrane element was produced and evaluated in the same manner as in Example 3.
- the inner resin part had a substantially elliptical shape with a major axis of 5.1 mm, a minor axis of 3.6 mm, a longitudinal interval of 5.6 mm, and a lateral interval of 3.7 mm. It was dot-like. Further, the cross-sectional shape of the inner resin portion was substantially rectangular.
- the water permeability of the separation membrane was 25.9 ⁇ 10 ⁇ 9 m 3 / m 2 / s / Pa, which was almost the same value as in Example 3.
- Table 1 shows the results of the area ratio of the resin part, the gap on the permeate side, and the water permeation performance.
- Example 8 Other than changing the size and vertical / horizontal spacing of the ethylene vinyl acetate copolymer resin so that the gap on the permeate side of the separation membrane is 2 mm (2000 ⁇ m) and the area ratio of the inner resin part is 67%
- the separation membrane element was produced and evaluated in the same manner as in Example 3.
- the inner resin portion was a substantially elliptical dot shape having a major axis of 11.7 m, a minor axis of 6.0 mm, and a vertical and horizontal interval of 0.7 mm. Further, the cross-sectional shape of the inner resin portion was substantially rectangular.
- the water permeability of the separation membrane was 24.0 ⁇ 10 ⁇ 9 m 3 / m 2 / s / Pa, which was a lower value than Example 3.
- Table 1 shows the results of the area ratio of the resin part, the gap on the permeate side, and the water permeation performance.
- Example 9 The separation membrane element was produced and evaluated in the same manner as in Example 3 except that the shape of the resin on the permeation side of the separation membrane was a stripe shape, and the area ratio of the inner resin portion was 31%.
- the resin part had a linear shape with a length of 99.7 mm, a width of 1.8 mm, and an interval of 5.0 mm in the width direction. Further, the cross-sectional shape of the inner resin portion was substantially rectangular.
- the water permeability of the separation membrane was 25.3 ⁇ 10 ⁇ 9 m 3 / m 2 / s / Pa, which was almost the same value as in Example 3. Table 2 shows the results of the area ratio of the resin part, the gap on the permeate side, and the water permeation performance.
- Example 11 The shape of the resin inside the permeation side of the separation membrane is a striped pattern of a striped steel plate, and a separation membrane element is produced and evaluated in the same manner as in Example 3 except that the area ratio of the resin portion inside is 10%.
- the inner resin portion was a striped pattern of a substantially rectangular striped strip with a length of 17.0 mm, a width of 1.7 mm, and a spacing of 6.7 mm.
- the cross-sectional shape of the inner resin portion was substantially rectangular.
- the water permeability of the separation membrane was 25.0 ⁇ 10 ⁇ 9 m 3 / m 2 / s / Pa, which was almost the same value as in Example 3.
- Table 2 shows the results of the area ratio of the resin part, the gap on the permeate side, and the water permeation performance.
- Example 12 The shape of the resin on the permeation side of the separation membrane is a striped pattern of a striped steel plate, and a separation membrane element is produced and evaluated in the same manner as in Example 11 except that the area ratio of the resin portion on the inner side is 34%.
- the inner resin portion was a striped pattern of a substantially rectangular striped strip having a length of 6.8 mm, a width of 3.2 mm, and a spacing of 1.6 mm.
- the cross-sectional shape of the inner resin portion was substantially rectangular.
- the water permeability of the separation membrane was 24.8 ⁇ 10 ⁇ 9 m 3 / m 2 / s / Pa, which was almost the same value as in Example 11.
- Table 2 shows the results of the area ratio of the resin part, the gap on the permeate side, and the water permeation performance.
- Example 13 The shape of the resin inside the permeation side of the separation membrane is a striped pattern of a striped strip, and the separation membrane element is produced and evaluated in the same manner as in Example 11 except that the area ratio of the resin portion inside is 59%.
- the inner resin portion was a striped pattern of a substantially rectangular striped strip with a length of 14.3 mm, a width of 3.2 mm, and an interval of 1.3 mm.
- the cross-sectional shape of the inner resin portion was substantially rectangular.
- the water permeability of the separation membrane was 24.2 ⁇ 10 ⁇ 9 m 3 / m 2 / s / Pa, which was slightly lower than Example 11. Table 2 shows the results of the area ratio of the resin part, the gap on the permeate side, and the water permeation performance.
- Example 1 A separation membrane element was produced and evaluated in the same manner as in Example 1 except that the resin was applied only around the permeation side of the separation membrane.
- the gap on the permeate side of the separation membrane is 0.4 mm or less (400 ⁇ m or less), and the water permeability of the separation membrane is 6.3 ⁇ 10 ⁇ 9 m 3 / m 2 / s / Pa, which is about 1 ⁇ 4 of that of Example 1.
- Value. Table 3 shows the results of the presence or absence of the resin part, the gap on the permeate side, and the water permeation performance.
- Example 2 Comparative Example 2 Except that the resin was applied only around the permeation side of the separation membrane, and further a net for the flow path (thickness: 700 ⁇ m, pitch: 5 mm ⁇ 5 mm, fiber diameter: 780 ⁇ m, projected area ratio: 30%) was sandwiched, A separation membrane element was produced and evaluated in the same manner as in Example 1.
- the water permeability of the separation membrane element was 16.2 ⁇ 10 ⁇ 9 m 3 / m 2 / s / Pa, which was about 3/5 of Example 1.
- Table 31 shows the results of the presence or absence of the resin part, the gap on the permeate side, and the water permeation performance.
- Example 15 As in Example 1, except that the height at which the ethylene vinyl acetate copolymer resin was applied and the thickness of the aluminum plate as the spacer were changed so that the gap on the permeate side of the separation membrane was 0.03 mm (30 ⁇ m).
- the water permeability of the separation membrane was 18.6 ⁇ 10 ⁇ 9 m 3 / m 2 / s / Pa, which was about 3/4 of that of Example 1.
- Table 3 shows the results of the area ratio of the resin part, the gap on the permeate side, and the water permeation performance.
- Example 16 A separation membrane element was prepared in the same manner as in Example 3 except that the size of the dot shape and the vertical and horizontal intervals to which the ethylene vinyl acetate copolymer resin was applied were changed so that the area ratio of the inner resin portion was 77%.
- the water permeability of the separation membrane was 17.6 ⁇ 10 ⁇ 9 m 3 / m 2 / s / Pa, which was about 5/7 of Example 1.
- Table 3 shows the results of the area ratio of the resin part, the gap on the permeate side, and the water permeation performance.
- Example 18 The resin temperature applied to the inner resin part on the permeate side of the separation membrane and the peripheral sealing part is changed to a modified olefin resin (trade name: EV165, softening point 105 ° C., manufactured by Toagosei Co., Ltd.)
- a separation membrane element was produced in the same manner as in Example 1 except that the temperature was 120 ° C. and the oven temperature was 95 ° C.
- the water separation performance of the obtained separation membrane element was 24.8 ⁇ 10 ⁇ 9 m 3 / m 2 / s / Pa, which was the same value as in Example 1.
- Example 19 The resin applied to the inner resin part on the permeate side of the separation membrane and the peripheral sealing part is changed to a thermoplastic rubber (trade name: SGH2005G, softening point 185 ° C., manufactured by Asahi Chemical Synthetic Co., Ltd.), and the resin temperature to be applied
- a separation membrane element was produced in the same manner as in Example 1 except that the temperature was set to 200 ° C. and the oven temperature was set to 170 ° C.
- the water separation performance of the obtained separation membrane was 24.8 ⁇ 10 ⁇ 9 m 3 / m 2 / s / Pa, which was the same value as in Example 1.
- Example 20 Comparative Example 5
- Durability was evaluated when the separation membrane elements described in Example 1, Example 2, Example 9, Example 12, and Comparative Example 2 were applied to MBR.
- the separation membrane element has the same structure as that for water permeability measurement described in Example 1 and Comparative Example 2, and has a substantially square shape of 50 cm square.
- the test method consists of 10 separation membrane elements bundled in parallel to form a separation membrane module, immersed in an activated sludge tank, with a water permeability of 0.3 m / day in the activated sludge and 15 L / min / element from the bottom. An aeration load was applied and the system was operated for about 3 months. It should be noted that the amount of aeration load is usually required to be minimal because it leads to energy costs during operation, and is generally 20 L / min / element or less.
- the separation membrane module using the separation membrane element of Example 1, Example 2, Example 9, and Example 12 has practical flexibility and rigidity without element breakage after about 3 months of testing. Had.
- the separation membrane module using the separation membrane element of Comparative Example 2 turbidity leakage due to element breakage occurred about one month after operation, and the flexibility and rigidity were insufficient.
- Example 21 As in Example 1, except that the height at which the ethylene vinyl acetate copolymer resin was applied and the thickness of the aluminum plate as the spacer were changed so that the gap on the permeate side of the separation membrane was 5.5 mm (5500 ⁇ m).
- the water permeability of the separation membrane was 25.1 ⁇ 10 ⁇ 9 m 3 / m 2 / s / Pa, which was almost the same value as in Example 1.
- a separation membrane module was produced in the same manner as in Example 20 for the separation membrane element obtained above and the separation membrane element of Example 4, and the durability was evaluated. Only the separation membrane element obtained above had wrinkles on the surface of the separation membrane. Although this separation membrane element was not damaged and no turbidity leakage was observed, there was a risk of damage during long-term operation starting with soot.
- a separation membrane module was produced by the same method as in Example 20, and the durability was evaluated by the method described in Reference Example 1. Only in the obtained separation membrane element, peeling of the inner resin portion and the separation membrane permeation side was confirmed. Although no turbidity leakage was observed in this separation membrane element, the separation membrane may be damaged during long-term operation.
- Example 23 Separation membrane element having a support plate made of ABS resin (conventional product) as a conventional product, separation membrane element having the configuration of the present invention (present invention), and a membrane module configured by arranging 100 separation membrane elements. Were made and compared. The results are shown in Table 4. The type of separation membrane used and the planar size (0.5 m ⁇ 1.4 m) were the same.
- the separation membrane element having the configuration of the present invention has the form schematically shown in FIG. 7, and the resin part is formed in a cylindrical shape having a diameter of about 3.0 mm and a height of about 2.5 mm.
- the periphery of the separation membrane was sealed with a sealing portion having a width of about 20 mm, and a water collecting portion having a width of about 35 mm was formed on a part of the periphery so as to be a combination of positions that did not overlap between adjacent separation membrane elements. .
- a water collection port made of polyethylene resin having the shape shown in FIGS. 9A and 9B was inserted into the water collection portion and then sealed.
- the separation membrane module having the configuration of the present invention is formed by forming a through hole (diameter of about 20 mm) at the end of the separation membrane element and passing the through rod through the through hole while arranging the adjacent water collecting ports so as not to overlap. Produced.
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Abstract
Description
(1)透過側の面が互いに対向するように配置された2枚の分離膜を有する分離膜対と、互いに対向する前記透過側の面の両方に接着する2個以上の樹脂部とを備え、前記分離膜対の周縁部が封止されていることを特徴とする分離膜エレメント。
(2)前記分離膜の周縁部の内側の面積に対する樹脂部の面積割合が、1%以上70%以下である(1)に記載の分離膜エレメント。
(3)前記分離膜対における前記分離膜の間隙が50μm以上5000μm以下である(1)または(2)に記載の分離膜エレメント。
(4)前記樹脂部が、軟化点が80~200℃である熱可塑性重合体で形成されている(1)から(3)のいずれかに記載の分離膜エレメント。
(5)前記樹脂部がドット状、線状、格子状のいずれかで配置されることを特徴とする(1)から(4)のいずれかに記載の分離膜エレメント。
(6)前記樹脂部が線状に配置され、線状部分が縞鋼板の縞模様に形成されていることを特徴とする(1)から(5)のいずれかに記載の分離膜エレメント。
(7)前記樹脂部の縞模様の縞目が前記分離対膜の周縁部に対して略平行および略垂直な方向に形成されていることを特徴とする(6)に記載の分離膜エレメント。
(8)周縁部の一部に集水部を設け、該集水部において周縁部の内側に形成された集水流路が外部と連通することを特徴とする(1)から(7)のいずれかに記載の分離膜エレメント。
(9)(1)から(8)のいずれかに記載の分離膜エレメントを複数平行に配列した分離膜モジュールであって、隣り合う分離膜エレメントの前記集水部同士が同じ位置にならないように配置されていることを特徴とする分離膜モジュール。
後述の方法で作成した分離膜を12cm角で2枚切り出し、各実施例、比較例に記載された方法で分離膜エレメントを作成した。得られた分離膜エレメントに、集水口のついた固定治具を取り付け、高さ20cm、幅20cm、奥行き20cm水槽に浸漬させ、水頭高さ1mで蒸留水を25℃で、5分間予備透過させた後、続けて蒸留水を透過させて透過水を5分間採取することにより透水量を測定する。
樹脂部が設けられた分離膜エレメントの内側を5cm角に切り出し、市販のスキャナーで画像を取り込み、この画像を明度差により2値化処理して、平面方向における個々の樹脂部の面積を測定した。この面積の総和を、膜表面に垂直な方向から樹脂部を投影した時に得られる投影面積とみなし、この投影面積を切り出した膜の面積(25cm2)で割った値(割合、面積%)を算出した。
分離膜エレメントを厚さ方向に切断した断面から2枚の分離膜の間隙をマイクロスコープ(キーエンス社製 型式:VHX-1100)で測定した。
樹脂部が設けられた分離膜エレメントの内側について、市販のスキャナーで画像を取り込み、この画像を明度差により2値化処理して、平面方向における個々の樹脂部の略形状を目視で判断した。個々の樹脂部については、樹脂部のみ(樹脂がない部分を含まない)の最長径の大きさをその樹脂部の長径、長径線の中心における垂直線(樹脂がない部分を含んでもよい)を短径とし、その平均値を算出した。なお、樹脂部の長径、短径の平均値は小数点2桁目を四捨五入した。
樹脂部が設けられた分離膜エレメントの内側について、市販のスキャナーで分離膜の表面に垂直な方向から見た画像を取り込み、この画像を明度差により2値化処理した後、個々の樹脂部について隣接する別の樹脂部との最短距離を測定し、その平均値を算出した。なお、樹脂部の間隔の平均値は小数点2桁目を四捨五入した。
分離膜エレメントを厚さ方向に切断した断面から、樹脂部の断面の略形状を目視で判断した。
製膜原液用の樹脂成分としてポリフッ化ビニリデン(PVDF、重量平均分子量28万)を用いた。また、開孔剤としてポリエチレングリコール(PEG20,000、重量平均分子量20,000)、溶媒としてN,N-ジメチルホルムアミド(DMF)、非溶媒としてH2Oをそれぞれ用いた。これらを95℃の温度下で十分に攪拌し、次の組成を有する製膜原液を作製した。
ポリフッ化ビニリデン(PVDF) :13.0重量%
ポリエチレングリコール(PEG20,000) : 5.5重量%
N,N-ジメチルホルムアミド(DMF) :78.0重量%
H2O : 3.5重量%
分離膜の透過側の間隙を0.05mm(50μm)となるように、エチレン酢酸ビニル共重合樹脂を塗布する高さと、スペーサーであるアルミ板の厚みを変更した以外は、実施例1と同様にエレメントを作製および評価したところ、内側の樹脂部は長径8.0mm、短径4.5mm、縦間隔4.0mm、横間隔2.5mmの略楕円形のドット状であり、その面積割合は35%であった(図1参照)。なお、内側の樹脂部の断面形状は略長方形状であった。分離膜の透水性能は24.6×10-9m3/m2/s/Paであり、実施例1より低い値であった。なお、樹脂部の面積割合、透過側の間隙、透水性能の結果を表1に示す。
分離膜の透過側の間隙を2mm(2000μm)となるように、エチレン酢酸ビニル共重合樹脂を塗布する高さと、スペーサーであるアルミ板の厚みを変更した以外は、実施例1と同様に分離膜エレメントを作製および評価したところ、内側の樹脂部は長径8.0mm、短径4.5mm、縦間隔4.0mm、横間隔2.5mmの略楕円形のドット状であり、その面積割合は35%であった(図1参照)。また、内側の樹脂部の断面形状は略長方形状であった。分離膜の透水性能は25.8×10-9m3/m2/s/Paであり、実施例1とほぼ同等の値であった。なお、樹脂部の面積割合、透過側の間隙、透水性能の結果を表1に示す。
分離膜の透過側の間隙を5mm(5000μm)となるように、エチレン酢酸ビニル共重合樹脂を塗布する高さと、スペーサーであるアルミ板の厚みを変更した以外は、実施例1と同様に分離膜エレメントを作製および評価したところ、内側の樹脂部は長径8.0mm、短径4.5mm、縦間隔4.0mm、横間隔2.5mmの略楕円形のドット状であり、その面積割合は35%であった(図1参照)。また、内側の樹脂部の断面形状は略長方形状であった。分離膜の透水性能は25.5×10-9m3/m2/s/Paであり、実施例1とほぼ同等の値であった。なお、樹脂部の面積割合、透過側の間隙、透水性能の結果を表1に示す。
内側の樹脂部の面積割合が1%となるように、エチレン酢酸ビニル共重合樹脂を塗布するドット形状の大きさおよび縦横間隔を変更した以外は、実施例1と同様に分離膜エレメントを作製および評価したところ、内側の樹脂部は長径1.1mm、短径1.1mm、縦間隔9.4mm、横間隔8.3mmの略円形のドット状であった。また、内側の樹脂部の断面形状は略楕円形状であった。分離膜の透水性能は24.7×10-9m3/m2/s/Paであり、実施例1とほぼ同等の値であった。なお、樹脂部の面積割合、透過側の間隙、透水性能の結果を表1に示す。
分離膜の透過側の間隙を2mm(2000μm)とし、内側の樹脂部の面積割合が5%となるように、エチレン酢酸ビニル共重合樹脂を塗布するドット形状の大きさおよび縦横間隔と、スペーサーであるアルミ板の厚みを変更した以外は、実施例3と同様に分離膜エレメントを作製および評価したところ、内側の樹脂部は長径2.6mm、短径1.8mm、縦横間隔7.5mmの略楕円形のドット状であった。また、内側の樹脂部の断面形状は略楕円形状であった。また、内側の樹脂部の断面形状は略長方形状であった。分離膜の透水性能は25.1×10-9m3/m2/s/Paであり、実施例3とほぼ同等の値であった。なお、樹脂部の面積割合、透過側の間隙、透水性能の結果を表1に示す。
分離膜の透過側の間隙を2mm(2000μm)とし、内側の樹脂部の面積割合が20%となるように、エチレン酢酸ビニル共重合樹脂を塗布するドット形状の大きさおよび縦横間隔を変更した以外は、実施例3と同様に分離膜エレメントを作製および評価したところ、内側の樹脂部は長径5.1mm、短径3.6mm、縦間隔5.6mm、横間隔3.7mmの略楕円形のドット状であった。また、内側の樹脂部の断面形状は略長方形状であった。分離膜の透水性能は25.9×10-9m3/m2/s/Paであり、実施例3とほぼ同等の値であった。なお、樹脂部の面積割合、透過側の間隙、透水性能の結果を表1に示す。
分離膜の透過側の間隙を2mm(2000μm)とし、内側の樹脂部の面積割合が67%となるように、エチレン酢酸ビニル共重合樹脂を塗布するドット形状の大きさおよび縦横間隔を変更した以外は、実施例3と同様に分離膜エレメントを作製および評価したところ、内側の樹脂部は長径11.7m、短径6.0mm、縦横間隔0.7mmの略楕円形のドット状であった。また、内側の樹脂部の断面形状は略長方形状であった。分離膜の透水性能は24.0×10-9m3/m2/s/Paであり、実施例3よりも低い値であった。なお、樹脂部の面積割合、透過側の間隙、透水性能の結果を表1に示す。
分離膜の透過側内側の樹脂の形状はストライプ形状で、内側の樹脂部の面積割合が31%となるようにした以外は、実施例3と同様に分離膜エレメントを作製および評価したところ、内側の樹脂部は長さ99.7mm、幅1.8mm、幅方向の間隔5.0mmの直線状であった。また、内側の樹脂部の断面形状は略長方形状であった。分離膜の透水性能は25.3×10-9m3/m2/s/Paであり、実施例3とほぼ同等の値であった。なお、樹脂部の面積割合、透過側の間隙、透水性能の結果を表2に示す。
分離膜の透過側内側の樹脂の形状はストライプ形状で、内側の樹脂部の面積割合が57%となるようにした以外は、実施例3と同様に分離膜エレメントを作製および評価したところ、内側の樹脂部は長さ10.1mm、幅3.7mm、幅方向の間隔3.5mmの直線状であった。また、内側の樹脂部の断面形状は略長方形状であった。分離膜の透水性能は24.1×10-9m3/m2/s/Paと僅かに、実施例9よりも低い値であった。なお、樹脂部の面積割合、透過側の間隙、透水性能の結果を表2に示す。
分離膜の透過側内側の樹脂の形状は縞綱板の縞模様で、内側の樹脂部の面積割合が10%となるようにした以外は、実施例3と同様に分離膜エレメントを作製および評価したところ、内側の樹脂部は長さ17.0mm、幅1.7mm、間隔6.7mmの略長方形の縞綱板の縞模様であった。また、内側の樹脂部の断面形状は略長方形状であった。分離膜の透水性能は25.0×10-9m3/m2/s/Paであり、実施例3とほぼ同等の値であった。なお、樹脂部の面積割合、透過側の間隙、透水性能の結果を表2に示す。
分離膜の透過側内側の樹脂の形状は縞綱板の縞模様で、内側の樹脂部の面積割合が34%となるようにした以外は、実施例11と同様に分離膜エレメントを作製および評価したところ、内側の樹脂部は長さ6.8mm、幅3.2mm、間隔1.6mmの略長方形の縞綱板の縞模様であった。また、内側の樹脂部の断面形状は略長方形状であった。分離膜の透水性能は24.8×10-9m3/m2/s/Paであり、実施例11とほぼ同等の値であった。なお、樹脂部の面積割合、透過側の間隙、透水性能の結果を表2に示す。
分離膜の透過側内側の樹脂の形状は縞綱板の縞模様で、内側の樹脂部の面積割合が59%となるようにした以外は、実施例11と同様に分離膜エレメントを作製および評価したところ、内側の樹脂部は長さ14.3mm、幅3.2mm、間隔1.3mmの略長方形の縞綱板の縞模様であった。また、内側の樹脂部の断面形状は略長方形状であった。分離膜の透水性能は24.2×10-9m3/m2/s/Paであり、実施例11より若干低い値であった。なお、樹脂部の面積割合、透過側の間隙、透水性能の結果を表2に示す。
分離膜の透過側内側の樹脂の形状は格子形状で、内側の樹脂部の面積割合が34%となるようにした以外は、実施例3と同様に分離膜エレメントを作製および評価したところ、内側の樹脂部は長径13.8mm、短径7.5mm、間隔3.4mmの略#字形をした格子ドット状であった。また、内側の樹脂部の断面形状は略長方形状であった。分離膜の透水性能は24.5×10-9m3/m2/s/Paであり、実施例1より低い値であった。なお、樹脂部の面積割合、透過側の間隙、透水性能の結果を表3に示す。
分離膜の透過側の周囲のみに樹脂を塗布した以外は、実施例1と同様に分離膜エレメントを作製および評価した。分離膜の透過側の間隙は0.4mm以下(400μm以下)であり、分離膜の透水性能は6.3×10-9m3/m2/s/Paと実施例1の1/4程度の値であった。なお、樹脂部の有無、透過側の間隙、透水性能の結果を表3に示す。
分離膜の透過側の周囲のみに樹脂を塗布し、さらに流路用のネット(厚み:700μm、ピッチ:5mm×5mm、繊維径:780μm、投影面積割合:30%)を挟み込んだこと以外は、実施例1と同様に分離膜エレメントを作製および評価をした。分離膜エレメントの透水性能は16.2×10-9m3/m2/s/Paと実施例1の3/5程度の値であった。なお、樹脂部の有無、透過側の間隙、透水性能の結果を表31に示す。
分離膜の透過側の間隙を0.03mm(30μm)となるように、エチレン酢酸ビニル共重合樹脂を塗布する高さと、スペーサーであるアルミ板の厚みを変更した以外は、実施例1と同様に分離膜エレメントを作製および評価したところ、分離膜の透水性能は18.6×10-9m3/m2/s/Paであり、実施例1の3/4程度の値であった。なお、樹脂部の面積割合、透過側の間隙、透水性能の結果を表3に示す。
内側の樹脂部の面積割合が77%となるように、エチレン酢酸ビニル共重合樹脂を塗布するドット形状の大きさおよび縦横間隔を変更した以外は、実施例3と同様に分離膜エレメントを作製および評価したところ、分離膜の透水性能は17.6×10-9m3/m2/s/Paであり、実施例1の5/7程度の値であった。なお、樹脂部の面積割合、透過側の間隙、透水性能の結果を表3に示す。
分離膜の透過側の内側の樹脂部と周縁の封止部に塗布する樹脂を、エチレン酢酸ビニル共重合樹脂(TEX YEAR INDUSTRIES INC.製、商品名:705AT、軟化点82℃)に変更し、塗布する樹脂温度を100℃、オーブンの温度を70℃とした以外は実施例1と同様の方法で分離膜エレメントを作製した。得られた分離膜エレメントの透水性能は24.7×10-9m3/m2/s/Paであり、実施例1とほぼ同等の値であった。
分離膜の透過側の内側の樹脂部と周縁の封止部に塗布する樹脂を、変成オレフィン系樹脂(東亞合成社製、商品名:EV165、軟化点105℃)に変更し、塗布する樹脂温度を120℃、オーブンの温度を95℃とした以外は実施例1と同様の方法で分離膜エレメントを作製した。得られた分離膜エレメントの透水性能は24.8×10-9m3/m2/s/Paであり、実施例1と同等の値であった。
分離膜の透過側の内側の樹脂部と周縁の封止部に塗布する樹脂を、熱可塑性ゴム(旭化学合成社製、商品名:SGH2005G、軟化点185℃)に変更し、塗布する樹脂温度を200℃、オーブンの温度を170℃とした以外は実施例1と同様の方法で分離膜エレメントを作製した。得られた分離膜の透水性能は24.8×10-9m3/m2/s/Paであり、実施例1と同等の値であった。
実施例1、実施例2、実施例9、実施例12、および比較例2に記載の分離膜エレメントをMBRに適用したときの耐久性を評価した。
実施例3と実施例12の分離膜エレメントをMBR適用したときの曝気に対する耐久性を比較した。
分離膜の透過側の間隙を5.5mm(5500μm)となるように、エチレン酢酸ビニル共重合樹脂を塗布する高さと、スペーサーであるアルミ板の厚みを変更した以外は、実施例1と同様に分離膜エレメントを作製および評価したところ、分離膜の透水性能は25.1×10-9m3/m2/s/Paであり、実施例1とほぼ同等の値であった。
分離膜の透過側の内側の樹脂部と周縁の封止部に塗布する樹脂を、オレフィン系樹脂(旭化学合成社製、商品名:AR1234、軟化点73℃)に変更し、塗布する樹脂温度を90℃、オーブンの温度を60℃とした以外は実施例1と同様の方法で分離膜エレメントを作製した。得られた分離膜の透水性能は24.9×10-9m3/m2/s/Paであり、実施例1とほぼ同等の値であった。
従来品としてABS樹脂製の支持板を有する分離膜エレメント(従来品)と、本発明の構成を有する分離膜エレメント(本発明)と、それぞれの分離膜エレメントを100枚配列して構成した膜モジュールを製作し比較した。その結果を表4に表す。なお、使用する分離膜の種類および平面サイズ(0.5m×1.4m)は同じとした。
2 分離膜
3 分離機能層
4 基材
5 間隙
6 封止部
7 内側の樹脂部
8 集水部
9 集水口
11 傾斜辺
12 分離膜モジュール
13 分離膜エレメント
14 分離膜浸漬水槽
15 散気装置
16 ブロア
17 吸引ポンプ
18 被処理水入口
19 被処理水出口
20 透過水
23 固定治具
24 集水管
Claims (9)
- 透過側の面が互いに対向するように配置された2枚の分離膜を有する分離膜対と、互いに対向する前記透過側の面の両方に接着する2個以上の樹脂部とを備え、前記分離膜対の周縁部が封止されていることを特徴とする分離膜エレメント。
- 前記分離膜の周縁部の内側の面積に対する樹脂部の面積割合が、1%以上70%以下である請求項1に記載の分離膜エレメント。
- 前記分離膜対における前記分離膜の間隙が50μm以上5000μm以下である請求項1または2に記載の分離膜エレメント。
- 前記樹脂部が、軟化点が80~200℃である熱可塑性重合体で形成されている請求項1から3のいずれかに記載の分離膜エレメント。
- 前記樹脂部がドット状、線状、格子状のいずれかで配置されることを特徴とする請求項1から4のいずれかに記載の分離膜エレメント。
- 前記樹脂部が線状に配置され、線状部分が縞鋼板の縞模様に形成されていることを特徴とする請求項1から5のいずれかに記載の分離膜エレメント。
- 前記樹脂部の縞模様の縞目が前記分離対膜の周縁部に対して略平行および略垂直な方向に形成されていることを特徴とする請求項6に記載の分離膜エレメント。
- 前記周縁部の一部に集水部を設け、該集水部において周縁部の内側に形成された集水流路が外部と連通することを特徴とする請求項1から7のいずれかに記載の分離膜エレメント。
- 請求項1から8のいずれかに記載の分離膜エレメントを複数平行に配列した分離膜モジュールであって、隣り合う分離膜エレメントの前記集水部同士が同じ位置にならないように配置されていることを特徴とする分離膜モジュール。
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JP2019502535A (ja) * | 2015-11-19 | 2019-01-31 | インテグリス・インコーポレーテッド | 多孔質膜上のフィーチャ |
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US11565217B2 (en) * | 2016-03-15 | 2023-01-31 | Solvay Specialty Polymers Italy S.P.A. | Composition and method for manufacturing sulfone polymer membrane |
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Also Published As
Publication number | Publication date |
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CN104245101A (zh) | 2014-12-24 |
KR20140130429A (ko) | 2014-11-10 |
US20150021260A1 (en) | 2015-01-22 |
JP6064902B2 (ja) | 2017-01-25 |
EP2818230B1 (en) | 2020-10-07 |
CN105921025A (zh) | 2016-09-07 |
EP2818230A4 (en) | 2015-11-04 |
CN104245101B (zh) | 2016-06-29 |
KR101966761B1 (ko) | 2019-04-08 |
CN105921025B (zh) | 2018-11-16 |
EP2818230A1 (en) | 2014-12-31 |
JPWO2013125506A1 (ja) | 2015-07-30 |
DK2818230T3 (da) | 2021-01-04 |
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