WO2021039846A1 - 分離膜エレメント - Google Patents
分離膜エレメント Download PDFInfo
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- WO2021039846A1 WO2021039846A1 PCT/JP2020/032195 JP2020032195W WO2021039846A1 WO 2021039846 A1 WO2021039846 A1 WO 2021039846A1 JP 2020032195 W JP2020032195 W JP 2020032195W WO 2021039846 A1 WO2021039846 A1 WO 2021039846A1
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- WIPO (PCT)
- Prior art keywords
- flow path
- supply
- separation membrane
- side flow
- fibrous
- Prior art date
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- OMOVVBIIQSXZSZ-UHFFFAOYSA-N [6-(4-acetyloxy-5,9a-dimethyl-2,7-dioxo-4,5a,6,9-tetrahydro-3h-pyrano[3,4-b]oxepin-5-yl)-5-formyloxy-3-(furan-3-yl)-3a-methyl-7-methylidene-1a,2,3,4,5,6-hexahydroindeno[1,7a-b]oxiren-4-yl] 2-hydroxy-3-methylpentanoate Chemical compound CC12C(OC(=O)C(O)C(C)CC)C(OC=O)C(C3(C)C(CC(=O)OC4(C)COC(=O)CC43)OC(C)=O)C(=C)C32OC3CC1C=1C=COC=1 OMOVVBIIQSXZSZ-UHFFFAOYSA-N 0.000 abstract 3
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Images
Classifications
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04B—KNITTING
- D04B1/00—Weft knitting processes for the production of fabrics or articles not dependent on the use of particular machines; Fabrics or articles defined by such processes
- D04B1/10—Patterned fabrics or articles
- D04B1/102—Patterned fabrics or articles with stitch pattern
-
- 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
- B01D63/10—Spiral-wound membrane modules
-
- 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
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04B—KNITTING
- D04B1/00—Weft knitting processes for the production of fabrics or articles not dependent on the use of particular machines; Fabrics or articles defined by such processes
- D04B1/22—Weft knitting processes for the production of fabrics or articles not dependent on the use of particular machines; Fabrics or articles defined by such processes specially adapted for knitting goods of particular configuration
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04B—KNITTING
- D04B21/00—Warp knitting processes for the production of fabrics or articles not dependent on the use of particular machines; Fabrics or articles defined by such processes
- D04B21/10—Open-work fabrics
- D04B21/12—Open-work fabrics characterised by thread material
-
- 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
- B01D2313/143—Specific spacers on the feed side
-
- 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
- B01D2325/00—Details relating to properties of membranes
- B01D2325/24—Mechanical properties, e.g. strength
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
- B01D65/08—Prevention of membrane fouling or of concentration polarisation
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2505/00—Industrial
- D10B2505/04—Filters
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Definitions
- the present invention relates to a separation membrane element for separating impurities from various liquids containing impurities, particularly for desalination of seawater, desalination of brine, production of ultrapure water, or wastewater treatment.
- Separation membranes used in the separation method using separation membrane elements are classified into microfiltration membranes, ultrafiltration membranes, nanofiltration membranes, reverse osmosis membranes and forward osmosis membranes in terms of their pore size and separation function. These membranes are used, for example, for the production of drinking water from seawater, irrigation water and water containing harmful substances, the production of industrial ultrapure water, wastewater treatment and recovery of valuable resources, and are intended for this purpose. It is used properly according to the separation component and separation performance.
- separation membrane elements There are various forms of separation membrane elements, but they are common in that raw water is supplied to one surface of the separation membrane and a permeated fluid is obtained from the other surface.
- the separation membrane element is provided with a large number of bundled separation membranes so that the membrane area per separation membrane element is large, that is, the amount of permeable fluid obtained per separation membrane element is large. It is formed to be.
- As the separation membrane element various shapes such as a spiral type, a hollow fiber type, a plate and frame type, a rotary flat membrane type, and a flat membrane integrated type have been proposed according to the application and purpose.
- a spiral separation membrane element is widely used for reverse osmosis filtration.
- the spiral type separation membrane element includes a water collecting pipe and a separation membrane unit wound around the water collecting pipe.
- the separation membrane unit is a supply-side flow path material that supplies raw water as supply water (that is, water to be treated) to the surface of the separation membrane, a separation membrane that separates components contained in the raw water, and a separation membrane that permeates the separation membrane from the supply-side fluid. It is formed by laminating a permeation side flow path material for guiding the separated permeation fluid to the water collecting pipe.
- the spiral type separation membrane element is preferably used because it can apply pressure to the raw water and can take out a large amount of permeated fluid.
- concentration polarization may occur in which dissolved substances such as salts in the feed water form a concentration gradient along the direction perpendicular to the separation membrane.
- concentration polarization for example, the thickness of the supply side flow path material is reduced, the film surface linear velocity of the supply water is increased, and the concentration polarization layer generated on the film surface is thinned. do it.
- the thickness of the flow path material on the supply side is reduced, impurities in the supply water and fouling substances due to microorganisms block the flow path on the supply side, which deteriorates the element performance and increases the pressure loss of the element.
- the required power of the pump that supplies the supply water becomes large, there are problems such as high power cost and damage to the element. Therefore, it has been proposed to improve the performance of the separation membrane element by using the flow path material on the supply side.
- Patent Documents 1 and 2 propose a net in which flow resistance is reduced by controlling the arrangement of fibrous substances in the flow path material on the supply side.
- Patent Document 3 devises a woven flow path material in which the warp and weft have a non-circular cross section.
- the present invention provides a separation membrane element capable of suppressing concentration polarization while suppressing blockage of the supply water inflow end face portion and the supply side flow path inside the element to reduce the flow resistance of the supply side flow path. Is the subject.
- a separation membrane element including at least a water collecting pipe, a separation membrane, a supply side flow path material, and a transmission side flow path material, wherein the supply side flow path material is provided.
- the supply-side flow path material is a plurality of fibers composed of fibrous materials A arranged in one direction. It is a net shape in which a plurality of fibrous rows Y composed of a fibrous material B, which are arranged in a direction different from that of the fibrous row X and the fibrous row X, intersect with each other to form an intersection.
- At least one of the fibrous material A and the fibrous material B has a large-diameter portion and a small-diameter portion along the longitudinal direction, and at least one of the fibrous material A and the fibrous material B is an arbitrary fiber.
- the central portion between the intersections of the fibrous row X and the fibrous row Y has a smaller diameter than the large diameter portion. It is composed of threads, has a supply-side flow path area ratio of 45 to 65%, and when observed in the thickness direction from the plane of the supply-side flow path material, fibers between arbitrary intersections and adjacent intersections are formed.
- a separation membrane element which is a tapered fiber whose diameter is tapered from one side to the other is provided. Further, according to a preferred embodiment of the present invention, there is provided a separation membrane element in which the taper ratio of the tapered fiber is in the range of 1/20 to 1/3. Further, according to a preferred embodiment of the present invention, there is provided a separation membrane element in which the tapered fibers are tapered from the raw water side toward the concentrated water side. Further, according to a preferred embodiment of the present invention, there is provided a separation membrane element having a rigidity (m) of 0.07 m or more and 0.14 m or less of the supply side flow path material.
- the ratio of the void volume v to the total volume V represented by the product of the thickness and the area of the supply side flow path material is 90 to 97%.
- a range of separation membrane elements is provided.
- a separation membrane element in which the ratio of the supply side flow path volume F of the separation membrane element to the void volume v of the supply side flow path material is 90% or more.
- a separation membrane element in which the distance between the intersections in the direction perpendicular to the raw water flow direction of the supply side flow path material is in the range of 3 to 5 mm.
- a separation membrane element in which the distance between the intersections in the direction parallel to the raw water flow direction of the supply side flow path material is in the range of 4 to 8 mm.
- the supply-side flow path material has the arbitrary fiber in a cross section Z in a direction perpendicular to the longitudinal direction of the arbitrary fibrous material of the supply-side flow path material.
- the maximum diameter W 2 in the direction perpendicular to the maximum diameter W 1 and the maximum diameter W 1 of Jo object is, 1.2 ⁇ W 1 / W 2 ⁇ 3.0 separation membrane element satisfies the relationship is provided .
- the transmission side flow path material is a circular knit tricot.
- the concentration polarization can be reduced while suppressing the increase in differential pressure due to the blockage of the supply side flow path, so that a separation membrane element having excellent operational stability can be obtained.
- the thickness of the flow path material on the supply side can be reduced, so that the filling membrane area per element, that is, the element water production amount can be increased.
- the fibrous material when the supply-side flow path material is observed from the plane in the thickness direction, the fibrous material has a tapered portion, so that rapid flow path expansion / contraction is reduced and flow resistance is reduced.
- the three-dimensional shape of the intersection of the fibers is gentle, damage to the membrane surface of the separation film can be suppressed.
- FIG. 1 is a partially developed perspective view showing an example of a separation membrane element.
- FIG. 2 is a plan view showing an example of the supply side flow path material of the present invention.
- FIG. 3 is a cross-sectional view showing an example of the supply side flow path material of the present invention.
- 4 (a) to 4 (c) are plan views showing an example of the supply-side flow path material of the present invention.
- 5 (a) and 5 (b) are plan views showing an example of a supply-side flow path material applied to other than the present invention.
- FIG. 6 is a plan view showing an example of the supply side flow path material of the present invention.
- 7 (a) and 7 (b) are cross-sectional views showing an example of the supply side flow path material of the present invention.
- FIG. 8 is a cross-sectional view showing an example of a supply-side flow path material applied to other than the present invention.
- 9 (a) to 9 (d) are views showing an example of a cross section obtained by cutting a fibrous material constituting the supply-side flow path material of the present invention.
- FIG. 10 is a diagram showing an example of a cross section obtained by cutting a fibrous material constituting the supply side flow path material of the present invention.
- the separation membrane element of the present invention includes at least a water collecting pipe, a separation membrane, a supply side flow path material, and a transmission side flow path material.
- a polymer net is used as the supply side flow path material 2 that forms the supply side flow path.
- the permeation side flow path material 4 a tricot having a finer interval than the supply side flow path material 2 is used for the purpose of preventing the separation membrane 3 from falling and forming a permeation side flow path.
- the envelope-shaped film 5 is formed by the permeation-side flow path material 4 and the separation film 3 which is overlapped on both sides of the permeation-side flow path material 4 and adhered in an envelope shape. The inside of the envelope-shaped membrane 5 constitutes a permeation-side flow path.
- the envelope-shaped membrane 5 alternately laminated with the supply-side flow path material 2 adheres a predetermined portion on the opening side to the outer peripheral surface of the water collecting pipe 6 and is surrounded in a spiral shape.
- the direction of the x-axis shown in FIG. 1 is the longitudinal direction of the water collecting pipe 6.
- the y-axis direction is perpendicular to the longitudinal direction of the water collecting pipe 6.
- the supply water 7 is usually supplied from one side surface, and the supply water 7 is gradually separated into the permeated water 8 and the concentrated water 9 while flowing in parallel with the water collecting pipe 6.
- the permeated water 8 goes out to the outside of the spiral type separation membrane element 1 from the opposite side surface to which the supply water 7 is supplied.
- the separation membrane element of the present invention shall be used for separation membrane elements of various shapes that use flat membranes such as plate-and-frame type and flat membrane integrated type, in addition to spiral type, depending on the application and purpose. Can be done.
- the supply-side flow path material of the present embodiment is different from the plurality of fibrous rows X composed of the fibrous material A (21) arranged in one direction and the fibrous rows X. It is composed of a plurality of fibrous rows Y composed of fibrous materials B (22) arranged in a direction, and the fibrous rows X and the fibrous rows Y intersect with each other to form intersections at a plurality of points. It has a net shape.
- the separation membrane element in order to suppress the concentration polarization that occurs on the surface of the separation membrane, it is important to reduce the retention points of the supply water, that is, the blockage points of the supply side flow path, and increase the degree of turbulence around the fibrous material. is there. This is because the turbulent flow supplies the surface of the separation membrane with supply water that has not yet come into contact with the membrane.
- the fibrous material that is not parallel to the flow direction of the supply water obstructs the flow of the supply water and increases the degree of turbulence. Fulfill.
- fibrous materials that are not parallel to the flow direction of the supply water block the flow path and obstruct the flow of the supply water, so that the flow resistance tends to increase. Therefore, either the fibrous material A or the fibrous material B is an intersection portion of the fibrous row X and the fibrous row Y in a vertical cross section along the longitudinal direction of the fibrous row including any fibrous row.
- the central part between the spaces is composed of threads with a smaller diameter than the intersection. This improves the balance between turbulence strength and flow resistance.
- the driving force for permeation is the intermembrane differential pressure, so it is effective to increase the intermembrane differential pressure in order to improve the amount of water produced.
- the intermembrane differential pressure is represented by subtracting the flow resistance and the osmotic pressure from the pressure applied to the separation membrane element. Therefore, in order to increase the intermembrane pressure, it is necessary to increase the applied pressure, decrease the flow resistance, or decrease the membrane osmotic pressure. Considering the case where the applied pressure is the same, the flow resistance or the osmotic pressure on the membrane surface may be lowered in order to improve the amount of water produced.
- the porosity of the flow path material on the supply side greatly affects the flow resistance.
- the porosity increases, the number of places where the fluid interferes decreases, so the flow resistance decreases, and when the porosity decreases, the number of places where the fluid interferes increases, so the flow resistance increases.
- the porosity is increased in an attempt to reduce the flow resistance, the amount of resin or the like constituting the supply-side flow path material is reduced, so that the rigidity of the supply-side flow path material is reduced. For example, a net in which the threads between the intersections are thin and necking (a phenomenon in which the polymer material does not stretch uniformly when the polymer material is stretched and a local constriction occurs after yielding) exists.
- the porosity is improved, which is advantageous in terms of flow resistance.
- the rigidity of such a net decreases, and the net expands and contracts, which makes it difficult to cut the net to a fixed length, and causes troubles during winding such as deterioration of the net's device passability. May cause.
- the rigidity of the net is reduced, which may cause troubles such as displacement of the net during element operation.
- At least one of the fibrous material A and the fibrous material B is composed of fibers having a large-diameter portion and a small-diameter portion along the longitudinal direction thereof and having a tapered portion. Is preferable.
- the taper will be described in "(Fiber shape)" below. Since at least one of the fibrous materials A and B is composed of tapered fibers, the rigidity of the flow path material on the supply side is maintained, and the rapid contraction / expansion of the fluid that causes an increase in flow resistance is suppressed. And the flow resistance can be reduced.
- One of the fibrous materials A and B may be a tapered fiber, or both may be a tapered fiber.
- the osmotic pressure increases as the concentration polarization generated on the surface of the separation membrane increases.
- the separation membrane element when the flow velocity of the supply water is slow, the fluid is separated from the membrane surface, or the fluid is difficult to flow before and after the fiber, the concentration polarization is increased. That is, in order to suppress the concentration polarization, it is effective to increase the membrane surface flow velocity or reduce the number of fibers in contact with the membrane surface. Therefore, in the vertical cross section including the arbitrary fibrous row, the fibrous material A and the fibrous material B have a smaller diameter at the central portion between the intersections of the fibrous row X and the fibrous row Y than the large diameter portion.
- the central portion between the intersection point of the fibrous array X and fibrous column Y, as shown in FIG. 3 as a code R 2 any of the fibrous materials A and fibrous material B, optionally of including a fibrous column, in longitudinal section along the longitudinal direction of the fibrous column, the time of the distance R 1 between adjacent two intersections P 10 equal parts, the other from one side of the intersection point P
- the range from 30% to 70% toward the intersection P that is, the range from the center point P 0 between the intersections P to 20% toward the adjacent intersections.
- the tapered shape in the present embodiment is specifically a tapered shape in which the diameter of the intersection formed by the fibrous material A and the fibrous material B and the fiber between the adjacent intersections expands from one to the other. Or it means that it has a thick tip.
- a tapered fiber is called a taper
- a fiber having a non-tapered shape and a uniform thread diameter is called a barrel
- a fiber having a necking is called a necking.
- the shape between the intersections of the fibrous rows in the supply side flow path materials 2a to 2c as shown in FIGS. 4 (a) to 4 (c) is tapered, and the supply side flow path as shown in FIG. 5 (a).
- the fibers may have a tapered shape from one side to the other when observed from a direction perpendicular to the plane of the supply side flow path material 2a. Due to the tapered shape, fluid separation from the yarn can be suppressed and flow resistance can be lowered.
- the tapered fibers taper in a certain direction, specifically from the supply water (raw water) side to the concentrated water side. The shape. With such a shape, it is possible to suppress the separation of the fluid from the yarn, prevent the rapid expansion and contraction of the fluid, and reduce the flow resistance.
- the webbing portion w is formed in the portion where the fibers overlap as shown in FIGS. 4 (b) and 4 (c).
- the “web portion” refers to a portion that is formed when the large diameter portions of the tapered fibers overlap each other and is wider than the central portion of the fibers in a plan view.
- the fiber has a tapered shape or a necking shape
- the amount of resin at the intersection increases, and the shape of the intersection becomes wider and smoother than that at the center, so that the film is less likely to be damaged.
- the removal rate does not easily decrease.
- necking since the yarn diameter is often small, it is easy to increase the area ratio of the flow path on the supply side, the porosity of the flow path material on the supply side is large, and the flow resistance can be lowered.
- the necking shape when compared with the tapered shape with the same flow path area ratio, in the necking shape, the flow path rapidly expands or contracts at the necking point, so that energy loss tends to occur and the differential pressure tends to increase. Further, since the necking shape has a large proportion of thin thread diameters, the rigidity tends to be low.
- the thickness L 4 of the intersections P overlapping the two threads in FIG 3 is the yarn diameter of the intersection portion, and the path between the intersection point
- the average thickness L 5 of the central portion R 2 in the above is the thread diameter of the central portion.
- the thread diameter (average thickness L 5 ) of the central portion R 2 is preferably 0.10 mm or more and 0.75 mm or less, more preferably 0.15 mm or more and 0.50 mm or less, and further preferably 0.20 mm or more. It is 0.40 mm or less.
- concentration polarization can be suppressed while reducing the flow resistance of the supply side flow path even when the thickness of the supply side flow path material is reduced, and the separation membrane. It is possible to improve the desalination rate and water production of the element.
- the thread diameter (thickness) at the intersection and the center can be measured by observing a vertical cross section parallel to the fibrous row with a commercially available microscope or X-ray CT measuring device and measuring the distance.
- the measurement mode can be used to measure the diameters of any 30 points at the intersection or the center, and use the measurement mode as the average value.
- the thickness of the feed-side passage material is substantially equivalent to the thickness L 4 of the intersection portion of the fibrous material A (21) and the fibrous material B (22). That is, it is the total thickness of the fibrous material A (21) and the fibrous material B (22). As shown in FIG. 3, the fibrous row X and the fibrous row Y are partially fused at the intersection.
- the average thickness of the supply-side flow path material is preferably 0.20 mm or more and 1.5 mm or less, more preferably 0.30 mm or more and 0.85 mm or less, and further preferably 0.50 mm or more and 0.80 mm or less. Is. If the average thickness of the flow path material on the supply side is within this range, the linear velocity of the supply water increases and the flow of the membrane surface is disturbed, so that the concentration polarization layer generated on the membrane surface becomes thin, and thus the element separation performance. Can be improved. Further, it is possible to suppress the blockage of the supply side flow path due to impurities in the supply water and foulants such as microorganisms, and to stably operate the separation membrane element for a long period of time without increasing the required power of the pump.
- the ratio "L 5 / L 4 " of the average thickness L 5 of the central portion to the thickness L 4 of the intersection portion is preferably 0.2 or more and 0.55 or less, and more preferably 0. It is .25 or more and 0.50 or less.
- the ratio of the yarn diameters at the intersection and the central portion is within this range, it is possible to increase the area ratio of the supply side flow path and sufficiently secure the supply side flow path inside the separation membrane element.
- the average thickness of the supply-side flow path material is the thickness of the intersection of 10 or more randomly selected fibrous materials A and B, that is, the total thickness of the fibrous material A and the fibrous material B.
- the variation in the thickness of the supply-side flow path material is preferably 0.9 times or more and 1.1 times or less the average thickness of the supply-side flow path material.
- the variation in the thickness of the flow path material on the supply side is within this range, the supply water can be uniformly supplied to the separation membrane element, so that the performance of the separation membrane can be uniformly exhibited.
- the supply-side flow path area ratio in the vertical cross section of any of the fibrous rows along the longitudinal direction is in the range of 45 to 65%.
- the supply-side flow path area ratio (%) is the ratio of the fibrous row including the fibrous row in the vertical cross section parallel to the fibrous row, based on the thickness of the intersection.
- the supply-side flow path area ratio is 45% or more, the flow resistance tends to decrease and the pressure loss tends to decrease. Further, if the area ratio of the flow path on the supply side is made higher than 65%, the ease of handling such that the device passability deteriorates and it becomes difficult to cut the fixed length dimension due to the decrease in the rigidity of the net, although it depends on the net material and the interval between the intersections.
- the flow velocity of the supplied water may decrease, the concentration polarization of the membrane surface may increase, and the desalting rate of the separation membrane element and the amount of water produced may decrease.
- the supply-side flow path area ratio can be taken as an average value by measuring the supply-side flow path area ratio at any 30 locations.
- the void volume of the supply-side flow path material of the present embodiment is the volume of a portion of the supply-side flow path material that can be a supply-side flow path.
- the void volume v of the supply-side flow path material is per cutout area (for example, 30 cm ⁇ 30 cm) with respect to the total volume V represented by the product of the thickness of the supply-side flow path material and the cut-out area of the supply-side flow path material.
- the volume of the supply-side flow path material is calculated by dividing the weight of the supply-side flow path material by the specific gravity of the supply-side flow path material, and is obtained by subtracting the volume of the supply-side flow path material from the total volume. be able to.
- the ratio of the void volume v of the supply side flow path material is preferably in the range of 90 to 97%. If the void volume v of the supply-side flow path material is within this range, the separation membrane element should have an improved balance between the turbulent flow strength of the supply water and the flow resistance without deteriorating the handleability of the supply-side flow path material. Can be done.
- the supply-side flow path volume of the separation membrane element of the present embodiment is the separation membrane element produced by using the supply-side flow path material, that is, the supply-side flow path material arranged between the two surfaces of the separation membrane. It is the volume of the part that can be the flow path on the supply side.
- the ratio of the supply-side flow path volume F of the separation membrane element to the void volume v of the supply-side flow path material is preferably 90% or more. When the ratio of the supply side flow path volume F of the separation membrane element to the void volume v of the supply side flow path material is 90% or more, the supply side flow path inside the separation membrane element is sufficiently secured, and the pressure due to the supply water flow Loss can be reduced.
- the measurement of the void volume v of the flow path material on the supply side is preferably performed by the X-ray CT measuring device in a non-destructive state, that is, in a state reflecting the influence of the membrane deformation at the time of manufacturing the separation membrane element. ..
- a non-destructive state that is, in a state reflecting the influence of the membrane deformation at the time of manufacturing the separation membrane element. ..
- cut the separation membrane element to a measurable size to make multiple parts and then shoot the part that is not affected by the cutting in the same way. It is also possible to adopt the method of doing.
- a cross-sectional image of the supply-side flow path material placed between the two surfaces of the separation membrane is obtained by X-ray CT measurement, and it is actually formed inside the separation membrane element by image analysis.
- the supply side flow path volume F is calculated.
- the cut-out area at the time of image analysis is the same as that at the time of measuring the void volume v of the flow path material on the supply side.
- the intersection interval (intersection period) c in the direction perpendicular to the supply water flow direction (raw water flow direction) of the supply side flow path material 2 shown in FIG. 2 is in the range of 3 to 5 mm. Is preferable, and more preferably the range is 3.5 to 4.5 mm. If the interval c at the intersections in the direction perpendicular to the supply water flow direction of the supply side flow path material is within this range, the phenomenon that the separation membrane falls into the void portion of the supply side flow path material can be suppressed when the separation membrane element is manufactured. In particular, it is possible to stably form a flow path of the supply water inflow end face portion.
- the interval d at the intersections in the direction parallel to the supply water flow direction of the supply side flow path material is preferably in the range of 4 to 8 mm, more preferably in the range of 4.5 to 6.0 mm. If the interval d between the intersections in the direction parallel to the supply water flow direction of the supply side flow path material is within this range, the balance between the turbulent flow strength of the supply water and the flow resistance can be achieved at the same time. And it is possible to improve the water production.
- the supply side flow path material can be observed from the upper part in the thickness direction (that is, the plane of the supply side flow path material), and the distance can be measured by, for example, a microscope.
- the angle is preferably 15 ° or more and 50 ° or less, and more preferably 30 ° or more and 45 ° or less.
- the ratio of the contact area of the supply-side flow path material to the separation membrane is preferably in the range of 0.05 to 0.2, and more preferably in the range of 0.1 to 0.15.
- the ratio of the contact area of the supply-side flow path material to the separation membrane is within this range, the supply water retention portion on the separation membrane surface can be reduced, and the supply water can be efficiently supplied to the separation membrane surface. Therefore, it is possible to improve the turbidity during operation and suppress troubles such as scale generation even when the operation is performed with a particularly high recovery rate.
- the thickness of the intersection is maintained by stretching and molding the supply side flow path material, which will be described later.
- the separation membrane element As a method of measuring the contact area ratio of the supply side flow path material to the separation membrane, the separation membrane element is disassembled, the separation membrane is cut out at a size of 5 cm ⁇ 5 cm, and the separation membrane is observed from the upper part in the thickness direction with a microscope to separate the separation membrane.
- the colored part of the pressure-sensitive paper is used as the contact part of the supply-side flow path material with the separation membrane, and the supply-side flow path material is analyzed by image analysis. Examples thereof include a method of calculating the ratio of the contact area to the separation membrane.
- the taper ratio is preferably 1/20 to 1/3, more preferably 1/15 to 1/4.
- the taper ratio is in this range, it is possible to suppress the fluid separation from the yarn, prevent the rapid expansion and contraction of the fluid, and reduce the flow resistance. If the taper rate exceeds 1/3, the taper rate is too high, so the intersections become large, the flow resistance becomes large, and the contact area with the film surface becomes too large, and the amount of scale adhesion tends to increase. ..
- FIG. 7 (Side shape of fiber) When observed from a direction parallel to the plane of the flow path material 2 on the supply side and perpendicular to an arbitrary fibrous material A or fibrous material B, the fibrous material A and the fibrous material are as shown in FIG. 7 (b). Even if the object B is tapered from one intersection P to the other intersection P, the thread diameter at the center between the intersections P is thin as shown in FIG. 7A. May be good.
- the shape of FIG. 7A is referred to as a different diameter
- the shape of FIG. 7B is referred to as a taper.
- FIG. 8 a shape in which the thread diameter does not become thin between the intersections is referred to as a barrel.
- the large-diameter portion in the present invention is a supply-side flow path material when observing, for example, the side surface of the fibrous material A (21) or the fibrous material B (22) in FIG.
- Two tangents of the cross section of the fibrous material B'adjacent to the fibrous material B in the direction perpendicular to the plane of the above are line segments passing through the fibrous material A, and are designated as a large diameter portion D 3 and a large diameter portion D 4, respectively.
- the central portion R 2 may be composed by small diameter fibers as compared to either of these.
- the thread diameter of the central portion / the thread diameter of the large diameter portion is preferably in the range of 0.9 to 0.2, and more preferably 0.8 to 0.3.
- the side shapes are not limited, and the shapes shown in FIGS. 7 (a) and 7 (b) can be mentioned as examples. It is possible to increase the porosity of the flow path material on the supply side, reduce the pressure loss, and suppress the adhesion of dirt substances and scales to the film surface.
- the cross-sectional shape of the fiber of the supply-side flow path material is preferably a flat shape or a streamlined shape as shown in FIGS. 9 (a) to 9 (d). A shape in which a part of these figures is missing may be used.
- the maximum diameter W 2 in the vertical direction preferably satisfies the relationship of 1.2 ⁇ W 1 / W 2 ⁇ 3.0, and the ratio W 1 / W 2 is in the range of 1.5 to 2.5. Is more preferable. If the ratio W 1 / W 2 is in the above range, the intersection is gentle, so that damage to the film surface during long-term operation can be suppressed, and if it is in this range, the flow path material on the supply side can be used. Since the flow path formed between the membranes gently expands or contracts, it is possible to suppress fluid separation from the membrane surface and suppress an increase in the concentration polarization of the dissolved salt.
- Maximum diameter W 1 and the maximum diameter W 2 of the vertical yarn diameter to said maximum diameter W 1 of the yarn diameter are any fibrous material in a direction perpendicular to the longitudinal direction, randomly selected 10 sites or more
- the cross section is an average value of values measured by a microscope, an X-ray CT measuring device, or the like, and can be calculated by the total of the measured values / the number of measurement points.
- the inclination angle of the cross section of the fiber of the supply side flow path material is defined below. As shown in FIG. 10, when the cross section of the supply side flow path material is observed from the raw water (supply water) side toward the concentrated water side, the flow side flow is parallel to the cross section of the supply side flow path material. a vertical line in a direction perpendicular to the road material is defined as the inclination angle of the angle formed in the clockwise maximum diameter W 1 and the perpendicular of any fibrous material. For example, when tilted at a right angle from the perpendicular, the tilt angle is 90 °.
- the inclination angle is preferably in the range of 10 ° to 170 °, more preferably in the range of 30 ° to 150 °. Within this range, it is possible to suppress fluid separation from the film surface while suppressing pressure loss.
- the inclination angle of the fiber can be set to an optimum angle from the balance between the differential pressure and the fluid separation of the film surface.
- the inclination angle is an average value of values measured by a microscope, an X-ray CT measuring device, or the like at 10 or more randomly selected cross sections in a direction perpendicular to the longitudinal direction of an arbitrary fibrous material. , It can be calculated by the total of the measured values / the number of measurement points.
- the basis weight of the supply-side flow path material is preferably in the range of 15 to 120 g / m 2. When the basis weight is within this range, the balance between the flow resistance and the protrusion or deviation of the net during long-term operation of the element is good, and the element performance can be improved.
- the basis weight of the supply side flow path material can be calculated by measuring the weight of at least 5 pieces of the supply side flow path material cut into a size of 1 m ⁇ 1 m and calculating the total of the measured values / the number of measured values.
- the variation in the basis weight of the supply-side flow path material is 0.9 times or more and 1.1 times or less of the average basis weight of the supply-side flow path material.
- the variation in the basis weight of the flow path material on the supply side is within this range, the supplied water can be uniformly supplied to the separation membrane element, so that the performance of the separation membrane can be uniformly exhibited.
- the rigidity and softness of the flow path material on the supply side is preferably in the range of 0.07 m to 0.14 m.
- the handleability of the supply side flow path material such as device passability and constant length cutting tends to be improved.
- the rigidity and softness of the supply-side flow path material exceeds 0.14 m, when surrounding the separation membrane unit in the spiral type separation membrane element, the end of the supply-side flow path material has a large curvature near the water collecting pipe. It rubs against the separation membrane, and the separation membrane is easily scratched.
- the rigidity and softness vary depending on the thickness and pitch of the supply side flow path material and the material of the supply side flow path material. By appropriately combining these, it is possible to manufacture a supply-side flow path material with good handleability. If the thickness of the flow path material on the supply side is too thin or the pitch is too wide, the rigidity will be less than 0.07 m, and if the thickness of the flow path material on the supply side is too thick or the pitch is too narrow, the rigidity will be soft. Exceeds 0.14m.
- the rigidity and softness of the flow path material on the supply side is measured based on JIS standard L1096 (2010) 8.21 (45 ° cantilever method). Specifically, select a flat place without curl for the supply side flow path material, and cut 5 test pieces into a size of 20 ⁇ 150 mm in the direction perpendicular to the longitudinal direction and the direction parallel to the longitudinal direction of the supply side flow path material, respectively. Prepare one by one. These test pieces are slid from a horizontal table, and the moving distance when the tip of the test piece touches a slope of 45 ° is the average value of the values measured with a ruler, etc., and the total of the measured values / the number of measurement points. Can be calculated with. When the test piece is curled, it is preferable to lightly press the test piece for 3 hours or more with a force that does not deform the test piece itself to remove the curl habit.
- the material of the flow path material on the supply side is not particularly limited, but a thermoplastic resin is preferable from the viewpoint of moldability, and polyethylene and polypropylene are particularly preferable because they are less likely to damage the surface of the separation membrane and are inexpensive. Further, in the supply side flow path material, the fibrous material A and the fibrous material B may be formed of the same material, or may be formed of different materials.
- the molding of the net-shaped supply side flow path material is generally performed by melting from an extruder while rotating the two inner and outer caps having a large number of holes arranged on the two inner and outer circumferences in opposite directions.
- the resin is supplied, and when or immediately after the resin comes out of the mouthpiece, the threads coming out of the inner and outer mouthpieces are crossed in a molten state and melted to form a network structure.
- the net takes a tubular shape. After that, the tubular net is cooled and solidified to determine the thickness, thread diameter, and interval between intersections, and then incised and taken as a sheet-shaped net.
- the supply-side flow path material has regions having different thread diameters in the fibrous material between the intersections while maintaining the thickness of the intersections, and the fiber shape is tapered when viewed from a plane.
- resin is supplied from a small base hole with a high resin discharge pressure, and before the resin of the tubular net is completely cooled and solidified, the inside of the tubular net has a diameter larger than the inner diameter of the tubular net. A method of allowing the tool to pass through and cooling and solidifying while simultaneously applying tension in the width direction and the longitudinal direction can be adopted.
- the net produced by passing a jig with a diameter larger than the inner diameter of the tubular net inside the tubular net is a gentle fiber from the intersection to the center.
- the feature is that the thread diameter of the shaped object becomes smaller.
- a jig with a diameter larger than the inner diameter of the tubular net is passed through the inside of the tubular net, and pulling is performed simultaneously in the width direction and the longitudinal direction at a lower ratio than the tapered supply side flow path material.
- a method of cooling and solidifying can be adopted.
- the thread diameter of the fibrous material in the central portion is necked with respect to the intersection. It is possible to manufacture a net having a different shape, and by observing the thread shape of the net, it is possible to determine the difference between the two manufacturing methods.
- the method for producing a net in which the central portion between the intersections of the fibrous rows is composed of threads having a smaller diameter than the intersections is not limited to these, and the intersections are formed by embossing, imprinting, pressing, or the like. It may be manufactured by a method of compressing and deforming a fibrous material between parts, a method of casting a molten resin on a mold and taking it out, and using a 3D printer.
- Transmission side flow path material In the envelope-shaped membrane 5, the separation membranes 3 are overlapped so that the surfaces on the transmission side face each other, and the transmission side flow path material 4 is arranged between the separation membranes 3, and the transmission side is transmitted by the transmission side flow path material 4. A flow path is formed.
- the material of the permeation side flow path material is not limited, and tricots, non-woven fabrics, porous sheets to which protrusions are fixed, films formed by concavo-convex molding and perforation processing, and concavo-convex non-woven fabrics can be used. Further, a protrusion functioning as a permeation side flow path material may be fixed to the permeation side of the separation membrane.
- the width of the needle loop and the width of the sinker loop can be made almost the same, and both loops can be used as a flow path, and also when the separation membrane element is operated. It is preferable in that the optimum flow path width in consideration of the film drop can be uniformly manufactured, and further, even if it is thin, a permeation side flow path material having sufficient pressure resistance and flow characteristics can be manufactured, so that the amount of water produced in the element can be improved.
- the separation membrane leaf may be formed by folding the separation membrane so that the supply side faces face inward, or two separate separation membranes are overlapped and separated so that the supply side faces face each other. It may be formed by sealing the periphery of the membrane.
- Examples of the "sealing" method include adhesion by an adhesive or hot melt, fusion by heating or laser, and a method of sandwiching a rubber sheet. Sealing by adhesion is particularly preferable because it is the simplest and most effective.
- the separation membrane element may be used as a separation membrane module by being connected in series or in parallel and housed in a pressure vessel.
- the above-mentioned separation membrane element and separation membrane module can be combined with a pump for supplying a fluid to them, a device for pretreating the fluid, and the like to form a fluid separation device.
- a separation device for example, the supplied water can be separated into permeated water such as drinking water and concentrated water that has not permeated the membrane, and water suitable for the purpose can be obtained.
- the operating pressure for permeating the supplied water is preferably 0.2 MPa or more and 5 MPa or less.
- the salt removal rate decreases as the supply water temperature increases, but the membrane permeation flux also decreases as the temperature decreases, so it is preferably 5 ° C or higher and 45 ° C or lower.
- the pH of the raw water is in the neutral region, even if the raw water is a liquid having a high salt concentration such as seawater, the generation of scales such as magnesium is suppressed, and the deterioration of the membrane is also suppressed.
- the water supplied to the separation membrane element of the present embodiment is not particularly limited, and may be pre-treated tap water or water having a large amount of impurities in the solution such as seawater and brackish water.
- the raw water (supply water) is a liquid mixture containing 500 mg / L or more and 100 g / L or less of TDS (Total Dissolved Solids) such as seawater, brackish water, and wastewater.
- TDS Total Dissolved Solids
- TDS Total Dissolved Solids
- a solution filtered through a 0.45 ⁇ m filter is evaporated at a temperature of 39.5 to 40.5 ° C. and can be calculated from the weight of the residue, but more simply it is converted from the practical salt content (S). ..
- the separation membrane element provided with the supply-side flow path material having a supply-side flow path area ratio in the range of 45 to 65% has few stagnation points formed before and after the fibrous material, so that the amount of water produced and the desalination rate are reduced. It is difficult to do, and it is difficult for scaling and fouling to occur.
- the separation membrane element of the present invention should be used in the subsequent stage of the vessel. Is preferable.
- the thinner the supply-side flow path material of the present invention the higher the cross-flow flow velocity, so that the risk of scaling and fouling can be reduced.
- image analysis of the vertical cross-sectional image was performed to calculate the area of the space formed between two adjacent intersections. Image analysis was performed at any 30 locations, and the average value was calculated.
- the supply-side flow path area ratio was calculated by (average area of space in the vertical section) / (average area between two adjacent intersections in the vertical section) ⁇ 100.
- volume v of the flow path material on the supply side A net-shaped sample was cut into 30 cm ⁇ 30 cm and its weight was measured. The total volume was calculated by multiplying the thickness of the flow path material on the supply side by the cut-out area. Next, the volume of the net-shaped sample body is calculated by dividing the weight of the cut-out net-shaped sample by the specific gravity of the supply-side flow path material, and the volume of the net-shaped sample body is reduced from the total volume to obtain the supply-side flow path. The void volume of the material was calculated.
- Intersection interval Using the high-precision shape measurement system KS-1100 manufactured by Keyence, observe the net-shaped sample from the upper part in the thickness direction at a magnification of 20 times, and supply the intersections in the direction perpendicular to the supply water flow direction of the supply side flow path material. With respect to the distance between the intersections in the direction parallel to the flow direction of the supply water of the side flow path material, 30 arbitrary intersections were measured and the average value was calculated.
- a net-shaped sample is frozen in liquid nitrogen, cut in a direction perpendicular to the longitudinal direction of any fibrous material, and the cross section is observed from a vertical direction using the high-precision shape measurement system KS-1100 manufactured by Keyence. and to measure the maximum diameter W 2 in the direction perpendicular to the maximum diameter W 1 and the maximum diameter W 1 of the cross section. The same operation was repeated at 15 places each of the arbitrary fibrous material A and the fibrous material B, and the average value was calculated.
- the net-shaped sample was cut into a size of 1.0 m ⁇ 1.0 m, the weight of 10 sheets was measured using an electronic balance, and the average value was calculated.
- the rigidity and softness of the flow path material on the supply side was measured based on JIS standard L1096 (2010) 8.21 (45 ° cantilever method).
- the net-shaped sample was cut into a size of 20 ⁇ 150 mm in the direction perpendicular to the longitudinal direction and the direction parallel to the longitudinal direction to obtain a test piece. If the test piece had curls, a plastic piece having the same size as the test piece was prepared, placed on the test piece, a weight of 200 g was placed on the test piece, and the test piece was allowed to stand for 3 hours. After that, 5 pieces of each were slid from the horizontal table at a constant speed, and the average value of the values measured with a ruler when the tip of the test piece touched the slope of 45 ° was calculated.
- a pressure-sensitive paper (two-sheet type model PSC-LLLW for prescale ultra-low pressure manufactured by FUJIFILM Corporation) is sandwiched between a polypropylene net as a flow path material on the supply side and a separation membrane to prepare a separation membrane element, and then separated. The membrane was disassembled and the pressure sensitive paper was collected. The colored portion of the pressure-sensitive paper was used as the contact portion of the supply-side flow path material with the separation membrane, and the contact area ratio of the supply-side flow path material with the separation membrane was calculated per 5 cm ⁇ 5 cm of the cutout area by image analysis.
- the surface of the polysulfone layer of the porous support membrane is immersed in an aqueous solution containing 1.5% by mass of m-PDA and 1.0% by weight of ⁇ -caprolactam for 2 minutes, and then slowly pulled up in the vertical direction. It was. Further, by blowing nitrogen from the air nozzle, excess aqueous solution was removed from the surface of the support membrane.
- n-decane solution containing 0.08% by mass of trimesic acid chloride was applied so that the surface of the film was completely wet, and then allowed to stand for 1 minute. Then, the excess solution was removed from the membrane by air blow and washed with hot water at 80 ° C. for 1 minute to obtain a composite separation membrane roll.
- the separation membrane thus obtained is folded and cut so that the effective area of the separation membrane element is 2.6 m 2, and a polypropylene net (thickness: 0.6 mm) shown in Table 1 is provided to the supply water side flow.
- a separation membrane leaf was prepared by sandwiching it as a road material.
- the tricot (thickness: 0.26 mm) shown in Table 1 is laminated on the permeation side surface of the obtained separation membrane leaf as a permeation side flow path material, and a leaf adhesive is applied to a PVC (polyvinyl chloride) water collecting pipe (polyvinyl chloride). Width: 1016 mm, diameter: 19 mm, number of holes 23 x linear 1 row) is spirally wound, the outer peripheral surface of the surrounding body is fixed with tape, edge cuts at both ends and end plate attachment are performed, and one side surface A separation membrane element having a diameter of 2.5 inches was prepared from which supply water was supplied and concentrated water was discharged.
- the separation membrane element is placed in a pressure vessel, and as feed water, a saline solution having a concentration of 200 ppm and a NaCl aqueous solution having a pH of 6.5 are used, and the operation is performed for 30 minutes under the conditions of an operating pressure of 0.5 MPa and a temperature of 25 ° C. for 1 minute. Sampling was performed and the amount of water permeation (gallon) per day was expressed as the amount of water produced (GPD (gallon / day)). The recovery rate was 8%.
- TDS removal rate 100 x ⁇ 1- (TDS concentration in permeated water / TDS concentration in feed water) ⁇
- the upstream side (supply water side) and downstream side (concentrated water side) of the cylindrical pressure vessel loaded with the separation membrane element are connected by piping via a differential pressure gauge (model DG16) manufactured by Nagano Keiki, and the element differential pressure during operation.
- the operating conditions were a supply water flow rate of 9 L / min, an operating pressure of 1.0 MPa, and reverse osmosis membrane treated water as the supply water.
- the cock of the permeated water pipe is closed, and the operation is performed in a state where membrane filtration cannot be substantially performed, that is, a state in which all the supplied water is discharged as concentrated water, and the element differential pressure (kPa). ) was measured.
- the separation membrane element is disassembled, the effective membrane portion on the downstream side (concentrated water side) in the longitudinal direction of the separation membrane element is cut out at a size of 5 cm ⁇ 5 cm, the cut out separation membrane is dried, and then microscopic from the upper part in the thickness direction of the separation membrane By observing with a scope, the ratio of the adhered area of the scale deposited on the membrane surface to the separation membrane surface was calculated.
- TDS removal rate (%) 100 x ⁇ 1- (TDS concentration in permeated water / TDS concentration in feed water) ⁇ The removal rate at this time was defined as the removal rate after starting and stopping.
- Example 1 The results were shown in Table 1 when the prepared supply-side flow path material was evaluated using the evaluation cell and the separation membrane element was placed in a pressure vessel under the above conditions.
- Examples 2 to 5, 7 to 27 Separation membrane elements were produced in the same manner as in Example 1 except that the supply-side flow path materials were as shown in Tables 1 to 4. When the separation membrane element was placed in a pressure vessel and each performance was evaluated under the same conditions as in Example 1, the results were shown in Tables 1 to 4.
- Example 6 The separation membrane element was produced in the same manner as in Example 1 except that the permeation side flow path material was as shown in Table 1. When the separation membrane element was placed in a pressure vessel and each performance was evaluated under the same conditions as in Example 1, the results were as shown in Table 1.
- Comparative Examples 1 and 2 the distance between the intersections in the direction perpendicular to and parallel to the supply water flow direction of the supply side flow path material is the same as in Examples 1 and 2, but the thread diameter in the central portion is large.
- the area ratio of the flow path on the supply side was low, the differential pressure of the element was high, and the amount of water produced by the element and the removal rate were reduced.
- the fiber shape and the side surface shape are small cylinders, the contact area between the film surface and the fiber is large, and the supply side flow path area ratio is low, so that the flow resistance is large and the element differential pressure is high. As a result, the amount of water produced in the element and the removal rate decreased.
- the supply-side flow path materials of Comparative Examples 1 to 3 have a high proportion of contact area with the separation membrane, and since there are many supply water retention sites on the separation membrane surface, the turbidity during operation is low, and the scale is on the separation membrane surface. Adhered a lot.
- Comparative Examples 4 and 5 since the fiber shape is necking and the rigidity and softness are small, the net is likely to be displaced when the start / stop operation is performed, and the removal rate after the start / stop is lowered. Further, in Comparative Examples 4 and 5, since the supply side flow path area ratio is too high, the film drops between the intersections of the supply side flow path materials, the element differential pressure becomes high, and the element water production amount and the removal rate decrease. It was.
- Comparative Example 6 the taper and the supply side flow path area ratio are the same, but since it has a necking shape, energy loss occurs due to the rapid expansion and contraction of the flow path, the element differential pressure becomes high, and the element There was a decrease in water production and removal rate.
- the membrane element of the present invention can be particularly suitably used for use as an RO water purifier, and for desalination of brine or seawater.
- Point Q 2 P 2 is connected to four adjacent diagonals, and the point where the diagonal line and the contour of the resin intersect and the point where the distance between P 2 is the largest L 1
- the distance between the two adjacent intersections Length of 1) L 2 Distance between two adjacent intersections (length of line segment P 2 Q 2 ) L 3 Line segment P 1 P 2 minus L 1 and L 2 Length L 4 Thickness of intersection L 5 Average thickness of center R 1 Distance between intersections when observed from the side R 2 Between intersections Central part C 1 L 1 Circle with radius C 2 L 2 with radius Circle D 1 P 1 P 2 perpendicular to and passing through C 1 tangent Fiber diameter D 2 P 1 P 2 perpendicular to C 2 tangent Fiber diameter D 3 thick diameter part (the tangent line of the cross section of the fibrous material B passes through the fibrous material A) D 4 thick diameter part (a line segment where the tangent line of the cross section of the fibrous material B'passes through the fibrous material A) W 1 Maximum diameter of the cross section
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- Textile Engineering (AREA)
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Abstract
Description
また、本発明の好ましい形態によれば、前記テーパー状繊維のテーパー率が1/20~1/3の範囲である分離膜エレメントが提供される。
また、本発明の好ましい形態によれば、前記テーパー状繊維が、原水側から濃縮水側に向かって先細りとなった形状である分離膜エレメントが提供される。
また、本発明の好ましい形態によれば、前記供給側流路材の剛軟度(m)が0.07m以上0.14m以下である分離膜エレメントが提供される。
また、本発明の好ましい形態によれば、前記供給側流路材は、前記供給側流路材の厚みと面積の積で表される総体積Vに対する空隙体積vの割合が90~97%の範囲である分離膜エレメントが提供される。
また、本発明の好ましい形態によれば、前記供給側流路材の空隙体積vに対する前記分離膜エレメントの供給側流路体積Fの割合が90%以上である分離膜エレメントが提供される。
また、本発明の好ましい形態によれば、前記供給側流路材の原水流れ方向に対して垂直方向の交点部の間隔が3~5mmの範囲である分離膜エレメントが提供される。
また、本発明の好ましい形態によれば、前記供給側流路材の原水流れ方向に対して平行方向の交点部の間隔が4~8mmの範囲である分離膜エレメントが提供される。
また、本発明の好ましい形態によれば、前記供給側流路材が、前記供給側流路材の任意の繊維状物の長手方向に対して垂直な方向の横断面Zにおいて、前記任意の繊維状物の最大径W1と前記最大径W1に対して垂直な方向の最大径W2が、1.2<W1/W2<3.0の関係を満たす分離膜エレメントが提供される。
また、本発明の好ましい形態によれば、前記透過側流路材が、丸編みトリコットである分離膜エレメントが提供される。
尚、本明細書において、「質量」は「重量」と同義である。また、本明細書において、「~」は、その前後に記載された数値を下限値および上限値として含むことを意味する。
本発明の分離膜エレメントは、少なくとも集水管と、分離膜と、供給側流路材と、透過側流路材とを備える。
(供給側流路材)
本実施形態の供給側流路材は、図2に示すように、一方向に並んだ、繊維状物A(21)から構成される複数の繊維状列X、および繊維状列Xとは異なる方向に並んだ、繊維状物B(22)から構成される複数の繊維状列Yから構成され、繊維状列Xと繊維状列Yとが互いに立体交差して複数の地点で交点を形成したネット形状をしている。
繊維状物A、Bの少なくとも一方がテーパー状の繊維で構成されることで、供給側流路材の剛性を保ちつつ、流動抵抗上昇の原因となる流体の急縮流・急拡流を抑制することができ、流動抵抗を低減できる。繊維状物A、Bは片方がテーパー状の繊維でもよいし、両方がテーパー状の繊維でもよい。
本実施形態におけるテーパー状とは、繊維状物Aと繊維状物Bが形成する交点と、隣り合う交点の間の繊維が一方から他方に向かって拡径している、具体的に、先細り形状または先太り形状になっていることを指す。ここでは、便宜上、テーパー状の繊維をテーパー、繊維が先細り形状になっておらず糸径が均一であるものを寸胴、交点間の繊維が細くなっており、ネッキングが存在する繊維をネッキングと呼称する。例えば、図4(a)~図4(c)に示すような供給側流路材2a~2cにおける繊維状列の交点間の形状がテーパー、図5(a)に示すような供給側流路材2dにおける繊維状列の交点間の形状が寸胴、図5(b)に示すような供給側流路材2eにおける繊維状列の交点間の形状がネッキングに当たる。
図4(a)に示したように、供給側流路材2aの平面に対して垂直な方向から観察したとき、繊維が一方から他方に先細り形状になっていればよい。先細り形状になっていることで、糸からの流体剥離を抑制し、流動抵抗を低くすることが出来る。好ましくは、図4(b)及び図4(c)に示したように、テーパー状の繊維が、一定の方向、具体的に供給水(原水)側から濃縮水側に向かって先細りとなった形状である。このような形状であれば、糸からの流体の剥離を抑制し、流体の急拡流および急縮流を防ぎ、流動抵抗を低減することが出来る。
また、ネッキングであると、糸径が細い割合が多いため、供給側流路面積率を上げやすく、供給側流路材の空隙率が大きくなり、流動抵抗を低くすることが出来る。しかし、テーパー形状と同一流路面積率で比較した場合、ネッキング形状であるとネッキング箇所で流路が急激に拡大もしくは縮小するため、エネルギー損失が起き、差圧が大きくなる傾向にある。さらに、ネッキング形状は糸径が細い割合が多いため、剛性が低くなりやすい傾向にある。
いずれかの繊維状列の長手方向に沿った当該繊維状列の縦断面において、図3における2本の糸が重なった交点部Pの厚みL4が交点部の糸径となり、また交点部間における中央部R2の平均厚みL5が中央部の糸径となる。
供給側流路材の厚みとは、実質的に繊維状物A(21)および繊維状物B(22)の交点部の厚みL4に相当する。すなわち、繊維状物A(21)と繊維状物B(22)の厚みの合計である。図3に示すように繊維状列Xおよび繊維状列Yは交点部分において部分的に融合する。
本実施形態では、いずれかの繊維状列の長手方向に沿った当該繊維状列の縦断面における供給側流路面積率が45~65%の範囲である。ここで供給側流路面積率(%)は、図3に示したように、繊維状列に平行な縦断面において、交点部の厚みに基づいて、繊維状列を含む、当該繊維状列の長手方向に沿った縦断面における空間の平均面積をA1、繊維状列の縦断面における隣接する2つの交点部間の平均面積をA2としたとき、A1/A2×100で表すことができる。供給側流路面積率が45%以上であると、流動抵抗が小さくなり圧力損失が減少する傾向がある。また供給側流路の面積率を65%より高くすると、ネット素材や交点部間隔にもよるが、ネットの剛性低下により、装置通過性が悪化したり定長寸法カットが困難になるといった取り扱い性が悪化したり、供給水の流速が低下して、膜面の濃度分極が増大し、分離膜エレメントの脱塩率や造水量が低下したりする原因となる場合がある。
本実施形態の供給側流路材の空隙体積とは、供給側流路材中の供給側流路となり得る部分の体積のことである。供給側流路材の空隙体積vは、供給側流路材の厚みと該供給側流路材の切り出し面積の積で表される総体積Vに対して、切り出し面積(例えば30cm×30cm)当たりの供給側流路材の重量を供給側流路材素材の比重で除することにより供給側流路材本体の体積を算出し、総体積から供給側流路材本体の体積を減ずることにより求めることができる。
本実施形態の分離膜エレメントの供給側流路体積とは、供給側流路材を使用して作製した分離膜エレメント、つまり分離膜の二つの面の間に配置された供給側流路材の供給側流路となり得る部分の体積のことである。供給側流路材の空隙体積vに対する分離膜エレメントの供給側流路体積Fの割合が90%以上であることが好ましい。供給側流路材の空隙体積vに対する分離膜エレメントの供給側流路体積Fの割合が90%以上であれば、分離膜エレメント内部の供給側流路が十分に確保され、供給水流れによる圧力損失を低減できる。
本実施形態では、図2に示す、供給側流路材2の供給水流れ方向(原水流れ方向)に対して垂直方向の交点部間隔(交点部周期)cが3~5mmの範囲であることが好ましく、さらに好ましくは3.5~4.5mmの範囲である。供給側流路材の供給水流れ方向に対して垂直方向の交点部間隔cがこの範囲であれば、分離膜エレメントの作製時に分離膜が供給側流路材の空隙部分に落ち込む現象を抑制でき、特に供給水流入端面部分の流路を安定に形成することが可能となる。
供給側流路材を平面から観察したとき、供給水流れ方向(すなわち集水管の長手方向)と繊維状物との角度が大きくなるにつれて乱流強度が増すものの、流動抵抗が増す傾向にある。よって、前記角度は15°以上50°以下が好ましく、30°以上45°以下が更に好ましい。
本実施形態では、供給側流路材の分離膜への接触面積割合が0.05~0.2の範囲であることが好ましく、さらに好ましくは0.1~0.15の範囲である。供給側流路材の分離膜への接触面積割合がこの範囲であれば、分離膜表面の供給水滞留部位を少なくでき、分離膜表面に効率的に供給水を供給できる。よって、運転時の排濁性を高め、特に高回収率で運転を行った場合においても、スケール発生等のトラブルを抑制することができる。
図6に示すように、供給側流路材2の平面を観察したとき、繊維状列Xと繊維状列Yが形成する多角形Sの対角同士を直線で結び、二つの直線が交じり合いかつ繊維がある箇所を繊維状列Xと繊維状列Yの糸の交点と定義する。交点に曲率がある場合も対角とみなす。
図6に示すように、任意の繊維の交点P1を決定する直線の延長線上かつ交点P1に最も近い4つの交点をB1~B4とする。線分P1B1~P1B4のうち、線と繊維の輪郭が交わる点のうち、P1との距離が最も大きくなる点Q1を選び、線分P1Q1の長さをL1とする。交点P1と隣り合う任意の交点P2に対して、交点P1と同様の作業を行い、点Q2を決定し、線分P2Q2の長さをL2とする。L1及びL2を半径とする円C1、C2を作成し、交点P1と交点P2を結ぶ直線の長さからL1とL2を引いた直線の長さをL3とする。線分P1P2に垂直かつ線分P1P2を通る円C1の接線と円C2の接線を作成し、それぞれの接線が形成する糸径をD1及びD2とする。テーパー率Tは、以下のように定義する。
供給側流路材2の平面に対して平行かつ、任意の繊維状物Aまたは繊維状物Bに垂直な方向から観察したとき、図7(b)に示すように繊維状物A及び繊維状物Bが片方の交点部Pからもう一方の交点部Pに向かってテーパー状になっていても、図7(a)に示すように交点部P間の中央部の糸径が細くなっていてもよい。便宜上、図7(a)の形状を異径、図7(b)の形状をテーパーと呼称する。また、図8のように、交点間で糸径が細くならない形状を寸胴と呼称する。
供給側流路材の繊維の断面形状としては、図9(a)~図9(d)に示すように扁平形状や流線形形状であることが好ましい。これらの図形の一部が欠けている形状でもよい。
供給側流路材の繊維の断面の傾斜角は、以下に定義するものである。図10に示したように、原水(供給水)側から濃縮水側に向かって供給側流路材の横断面を観察したとき、供給側流路材の横断面に対して平行かつ供給側流路材に対して垂直な方向に垂線を引き、任意の繊維状物の最大径W1と前記垂線の時計回りになす角を傾斜角と定義する。例えば、垂線から直角に傾斜している場合、傾斜角は90°となる。この傾斜角は、10°~170°の範囲が好ましく、さらに好ましくは30°~150°の範囲である。この範囲であれば、圧力損失を抑制しつつ、膜面からの流体剥離を抑制することができる。繊維の傾斜角は、差圧や膜面の流体剥離のバランスから、最適な角度を設けることができる。
供給側流路材の目付量は、15~120g/m2の範囲であることが好ましい。目付量がこの範囲であることで、流動抵抗とエレメント長期運転時のネットの飛び出しやズレのバランスが良く、エレメント性能を向上させることが出来る。
供給側流路材の剛軟度は、0.07m~0.14mの範囲であることが好ましい。供給側流路材の剛軟度が0.07m以上であると、供給側流路材の装置通過性や定長寸法カットといった取り扱い性が良くなる傾向がある。供給側流路材の剛軟度が0.14mを超えると、スパイラル型分離膜エレメントにおいて、分離膜ユニットを巻囲する際、集水管に近い曲率が大きいところで供給側流路材の端部が分離膜に擦れ、分離膜に傷が入りやすくなる。剛軟度は、供給側流路材の厚みやピッチ、供給側流路材の素材によって変化する。これらを適切に組み合わせることで、ハンドリング性の良い供給側流路材の作製が可能である。供給側流路材の厚みが薄すぎたり、ピッチが広すぎたりすると、剛軟度が0.07mを下回り、供給側流路材の厚みが分厚すぎたり、ピッチが狭すぎたりすると剛軟度が0.14mを上回る。
供給側流路材の素材は特に限定されないが、成形性の観点から熱可塑性樹脂が好ましく、特にポリエチレンおよびポリプロピレンは分離膜の表面を傷つけにくく、また安価であるので好適である。また、供給側流路材は、繊維状物Aと繊維状物Bが同じ素材で形成されても構わないし、異なる素材で形成されていても構わない。
ネット状の供給側流路材の成形は、一般的に内側と外側の2つの円周上に多数の孔を配置した内側と外側の2つの口金を逆方向に回転させながら、押出機から溶融させた樹脂を供給して、樹脂が口金から出る時または出た直後に内側と外側の口金から出る糸を溶融状態で交差させて溶融し網状構造を形成する。この段階ではネットは筒状の形状を取る。その後筒状のネットは冷却固化により厚みや糸径、交点部間隔を決定後、切開されてシート状ネットとして引き取られる。
(透過側流路材)
封筒状膜5において、分離膜3は透過側の面を対向させて重ね合わされており、分離膜3同士の間には透過側流路材4が配置され、透過側流路材4によって透過側流路が形成される。透過側流路材の材料としては限定されず、トリコットや不織布、突起物を固着させた多孔性シート、凹凸成形し、穿孔加工を施したフィルム、凹凸不織布を用いることができる。また、透過側流路材として機能する突起物を分離膜の透過側に固着させてもよい。
中でも、丸編機により製造された丸編みトリコットを用いると、ニードルループの幅とシンカーループの幅とをほぼ同一にし、どちらのループをも流路として使用できるだけでなく、分離膜エレメントの運転時の膜落ち込みを考慮した最適な流路幅を均一に製造でき、さらに、薄くても十分な耐圧性と流動特性を併せ持つ透過側流路材を製造できるためエレメント造水量を向上させる点で好ましい。
分離膜リーフは、供給側の面が内側を向くように分離膜を折りたたむことで形成されてもよいし、別々の2枚の分離膜を、供給側の面が向かい合うようにして重ね合わせ、分離膜の周囲を封止することで形成されてもよい。
分離膜エレメントは、直列または並列に接続して圧力容器に収納されることで、分離膜モジュールとして使用されてもよい。
本実施形態の分離膜エレメントへの供給水は特に限定されず、予め処理された水道水でもよく、海水やかん水のように溶液中の不純物が多いものでもよい。例えば、水処理に使用する場合、原水(供給水)としては、海水、かん水、排水等の500mg/L以上100g/L以下のTDS(Total Dissolved Solids:総溶解固形分)を含有する液状混合物が挙げられる。一般に、TDSは総溶解固形分量を指し、「質量÷体積」で表されるが、1Lを1kgと見なして「重量比」で表されることもある。定義によれば、0.45μmのフィルターで濾過した溶液を39.5~40.5℃の温度で蒸発させ残留物の重さから算出できるが、より簡便には実用塩分(S)から換算する。
キーエンス社製高精度形状測定システムKS-1100を用い、ネット状サンプルの繊維状列に平行な縦断面を倍率20倍で観察し、交点部および中央部の糸径をそれぞれ確認した。具体的には、交点部については任意の交点部の中心部の糸径を30カ所、中央部については隣接する2つの交点部間の中心点からそれぞれ隣接する交点に向かって20%までの範囲の任意の30カ所の糸径を計測して、その平均値を算出した。
キーエンス社製高精度形状測定システムKS-1100を用い、ネット状サンプルの繊維状列に平行な縦断面を倍率20倍で観察し、任意の交点部分の厚みを30カ所測定し、その平均値を算出した。
キーエンス社製高精度形状測定システムKS-1100を用い、供給側流路材の繊維状列に平行な縦断面を倍率20倍で観察し、隣接する2つの交点部間距離と交点厚み(供給側流路材厚み)をそれぞれ30カ所測定しその平均値を算出した。隣接する2つの交点部間距離に交点厚みを乗じて縦断面における隣接する2つの交点部間の面積を算出した。
ネット状サンプルを30cm×30cmに切り取りその重量を計測した。供給側流路材の厚みに切り出し面積を乗じて総体積を算出した。次いで、切り出したネット状サンプルの重量を供給側流路材素材の比重で除してネット状サンプル本体の体積を算出し、総体積からネット状サンプル本体の体積を減ずることにより、供給側流路材の空隙体積を算出した。
スパイラル型分離膜エレメントを長さが30cmの筒状になるように切断した後、ヤマト科学株式会社製三次元計測X線CT装置(TDM3000H-FP)でスパイラル型分離膜エレメントをX線強度100kVで撮影し、分離膜の二つの面の間に配置された切り出し面積30cm×30cmあたりのネット状サンプルの供給側流路となり得る部分の体積(内部体積)を画像解析により算出した。
キーエンス社製高精度形状測定システムKS-1100を用い、ネット状サンプルを厚み方向上部から倍率20倍で観察し、供給側流路材の供給水流れ方向に対して垂直方向の交点部間隔と供給側流路材の供給水流れ方向に対して平行方向の交点部間隔について、任意の交点部間隔を30カ所測定し、その平均値を算出した。
キーエンス社製高精度形状測定システムKS-1100を用い、ネット状サンプルを平面方向から撮影し、パワーポイントを用いて画像上に作図を行った。任意の多角形Sの対角同士を直線で結び、交点P1を決定した。交点P1を決定する直線の延長線上かつ交点P1に最も近い4つの交点をB1~B4とし、線分P1B1~P1B4のうち、線と繊維の輪郭が交わる点のうち、P1との距離が最も大きくなる点Q1を選び、線分P1Q1の長さをL1とした。交点P1と隣り合う任意の交点P2に対して、交点P1と同様の作業を行い、点Q2を決定し、線分P2Q2の長さをL2とした。L1及びL2を半径とする円C1、C2を作成し、交点P1と交点P2を結ぶ直線の長さからL1とL2を引いた直線の長さをL3とした。線分P1P2に垂直かつ線分P1P2を通る円C1の接線と円C2の接線を作成し、それぞれの接線が形成する糸径をD1及びD2とした。キーエンス社製高精度形状測定システムKS-1100によって得られた画像のスケールバーを基に、L1~L3、D1、D2の長さを計測し、下記式に基づきテーパー率Tを算出した。この操作を、供給側流路材の表裏の面にそれぞれ15カ所、合計30カ所測定し、その平均値を算出した。
繊維状物Aもしくは繊維状物Bの細径の繊維で構成されている方を選び、例えば、繊維状物Aを選んだとき、ネット状サンプルを液体窒素で凍結させ、繊維状物Aと平行な方向かつ繊維状物A近傍で繊維状物Bをカットした。キーエンス社製高精度形状測定システムKS-1100を用い、ネット状サンプルの平面に対して平行かつ、任意の繊維状物Aまたは繊維状物Bに垂直な方向から倍率20倍で観察し、太径部D3、D4の糸径を確認した。具体的には、太径部は任意の太径部D3、D4の糸径を測定し、大きい方を太径部とした。この操作を合計30カ所について行い、それらの平均値を算出した。
ネット状サンプルを液体窒素で凍結させ、任意の繊維状物の長手方向に対して垂直な方向にカットし、キーエンス社製高精度形状測定システムKS-1100を用い、横断面を垂直な方向から観察し、横断面の最大径W1及び当該最大径W1に垂直な方向の最大径W2を測定した。任意の繊維状物A及びの繊維状物Bのそれぞれ15カ所について同様の操作を繰り返し、その平均値を算出した。
ネット状サンプルを液体窒素で凍結させ、任意の繊維状物の長手方向に対して垂直な方向にカットし、キーエンス社製高精度形状測定システムKS-1100を用い、横断面を垂直な方向から観察し、垂線と横断面の最大径W1との時計回りになす角を測定した。任意の繊維状物A及びの繊維状物Bのそれぞれ15カ所について同様の操作を繰り返し、その平均値を算出した。
ネット状サンプルを1.0m×1.0mの大きさにカットし、電子天秤を用いて10枚の重量を測定し、平均値を算出した。
供給側流路材の剛軟度は、JIS規格L1096(2010)8.21(45°カンチレバー法)を基に測定した。ネット状サンプルを、長手方向に垂直な方向及び平行な方向に20×150mmのサイズにカットし、試験片とした。試験片にカールがある場合は、試験片と同じ大きさのプラスチック片を用意し、試験片の上に乗せ、その上に200gの重りを置いて、3時間静置した。その後、それぞれ5片ずつを水平台上から一定速度で滑らせ、45°の斜面坂に試験片の先端が接したときの移動距離を定規で測定した値の平均値を算出した。
供給側流路材としてのポリプロピレン製ネットと分離膜との間に感圧紙(富士フイルム株式会社製 ツーシートタイプ 型式PSC-LLLW プレスケール極超低圧用)を挟み込んで分離膜エレメント作製し、その後分離膜を解体して感圧紙を回収した。感圧紙の発色した部分を供給側流路材の分離膜への接触部分とし、画像解析により切り出し面積5cm×5cmあたり供給側流路材の分離膜への接触面積割合を算出した。
(供給側流路材Pの作製)
ポリプロピレンを材料として、多数の小さい孔を配置した内側と外側の2つの口金を逆方向に回転させながら、押出機から溶融させた樹脂を高い吐出圧で供給して、網状構造を有する筒状ネットを成形した。さらに筒状のネットの樹脂が完全に冷却固化する前に筒状ネットの内側に、筒状ネットの内径より径の大きい治具を通過させて、幅方向および長手方向に同時に引っ張りを加えながら冷却固化させる方法により、交点部から中央部にかけてなだらかに繊維状物の糸径が細くなる形状の、表1~表5に示す供給側流路材を作製した。なお、押出機からの溶融樹脂吐出圧、筒状ネットを通過させる治具の寸法、引き取り速度を変更し、最終的に表1~表5の供給側流路材形状となるよう構造制御を行った。
ポリエチレンテレフタレート繊維からなる不織布(繊度:1デシテックス、厚み:約90μm、通気度:1cc/cm2/sec、密度0.80g/cm3)上にポリスルホンの16.0質量%のDMF溶液を180μmの厚みで室温(25℃)にてキャストし、ただちに純水中に浸漬して5分間放置し、80℃の温水で1分間浸漬することによって繊維補強ポリスルホン支持膜からなる、多孔性支持層(厚さ130μm)ロールを作製した。
分離膜エレメントを圧力容器に入れて、供給水として、濃度200ppmの食塩水、pH6.5のNaCl水溶液を用い、運転圧力0.5MPa、温度25℃の条件下で30分間運転した後に1分間のサンプリングを行い、1日あたりの透水量(ガロン)を造水量(GPD(ガロン/日))として表した。なお、回収率は8%とした。
造水量の測定における1分間の運転で用いた供給水およびサンプリングした透過水について、TDS濃度を伝導率測定により求め、下記式からTDS除去率を算出した。
TDS除去率(%)=100×{1-(透過水中のTDS濃度/供給水中のTDS濃度)}
分離膜エレメントを装填する円筒状圧力容器の上流側(供給水側)と下流側(濃縮水側)を長野計器製差圧計(型式DG16)を介して配管で接続し、運転中のエレメント差圧を計測した。運転条件は、供給水流量は9L/分、運転圧力は1.0MPaとし、供給水には逆浸透膜処理水を用いた。また、エレメント内部の気泡が抜けた後は透過水配管のコックを閉じ、実質的に膜ろ過が行えない状態、つまり供給水が全量濃縮水として排出される状態で運転を行いエレメント差圧(kPa)の測定を行った。
分離膜エレメントを圧力容器に入れて、供給水として、1150ppmのCaCl2・2H2O、660ppmのNaHCO3、pH7の水溶液を用い、運転圧力0.5MPa、温度25℃の条件下で24時間運転した。なお、回収率は50%とした。その後、分離膜エレメントを解体して分離膜エレメントの長手方向の下流側(濃縮水側)の有効膜部分を5cm×5cmで切り出し、切り出した分離膜を乾燥後、分離膜の厚み方向上部からマイクロスコープにより観察し、膜面に析出したスケールの分離膜表面への付着面積割合を算出した。
作製した分離膜エレメントについて、供給水として、濃度200ppmの食塩水、pH6.5のNaCl水溶液を用い、運転圧力0.5MPa、温度25℃の条件下で1分間×100回通水した。その後、1分間のサンプリングを行い、1分間の運転で用いた供給水およびサンプリングした透過水について、TDS濃度を伝導率測定により求め、下記式からTDS除去率を算出した。
TDS除去率(%)=100×{1-(透過水中のTDS濃度/供給水中のTDS濃度)}
このときの除去率を発停後除去率とした。
作製した供給側流路材について評価セルを用い、また分離膜エレメントを圧力容器に入れて、上述の条件で評価したところ、結果は表1の通りであった。
供給側流路材を表1~4の通りにした以外は全て実施例1と同様にして、分離膜エレメントを作製した。
分離膜エレメントを圧力容器に入れて、実施例1と同条件で各性能を評価したところ、結果は表1~4の通りであった。
透過側流路材を表1の通りにした以外は全て実施例1と同様にして、分離膜エレメントを作製した。
分離膜エレメントを圧力容器に入れて、実施例1と同条件で各性能を評価したところ、結果は表1の通りであった。
(供給側流路材Qの作製)
ポリプロピレンを材料として、多数の孔を配置した内側と外側の2つの口金を逆方向に回転させながら、押出機から溶融させた樹脂を供給して、網状構造を有する筒状ネットを成形し、繊維形状が寸胴であるネットを製造した。なお、押出機からの溶融樹脂吐出圧、引き取り速度を変更し、最終的に表4、5の供給側流路材形状となるよう構造制御を行った。
ポリプロピレンを材料とし、供給側流路材Qと同様の手順で作製した筒状のネットを一旦冷却固化させ、その後、加熱炉内で縦延伸次いで横延伸を逐次で行い、交点部に対し中央部の繊維状物の糸径がネッキングした形状のネットを製造した。なお、押出機からの溶融樹脂吐出圧、縦および横の延伸倍率、引き取り速度を変更し、最終的に表5の供給側流路材形状となるよう構造制御を行った。
供給側流路材を表4~5の通りにした以外は全て実施例1と同様にして、分離膜エレメントを作製した。
分離膜エレメントを圧力容器に入れて、上述の条件で各性能を評価したところ、結果は表4、5の通りであった。
また、比較例1~3の供給側流路材は分離膜への接触面積割合が高く、分離膜表面の供給水滞留部位が多いことから運転時の排濁性が低く、分離膜表面にスケールが多く付着した。
また、比較例4、5は供給側流路面積率が高すぎるため、供給側流路材の交点間で膜落ち込みが生じ、エレメント差圧が高くなり、エレメント造水量と除去率の低下が生じた。
2 供給側流路材
2a~2e 供給側流路材
21 繊維状物A
22 繊維状物B
3 分離膜
4 透過側流路材
5 封筒状膜
6 集水管
7 供給水
8 透過水
9 濃縮水
c 供給側流路材の供給水流れ方向に対して垂直方向の交点部間隔
d 供給側流路材の供給水流れ方向に対して平行方向の交点部間隔
w 水かき部
A1 繊維状列に平行な縦断面における空間の面積
A2 繊維状列に平行な縦断面における隣接する2つの交点部間の面積
P 交点部
P0 交点部間の中心点
P1 任意の繊維の交点
P2 P1と隣り合う交点
B1 交点P1を決定する直線の延長線上かつ交点P1に最も近い交点の一つ
B2 交点P1を決定する直線の延長線上かつ交点P1に最も近い交点の一つ
B3 交点P1を決定する直線の延長線上かつ交点P1に最も近い交点の一つ
B4 交点P1を決定する直線の延長線上かつ交点P1に最も近い交点の一つ
Q1 P1と隣接する4つの対角を結び、対角線と樹脂の輪郭が交わる点とP1の距離が最も大きくなる点
Q2 P2と隣接する4つの対角を結び、対角線と樹脂の輪郭が交わる点とP2の距離が最も大きくなる点
L1 隣接する2つの交点部間距離(線分P1Q1の長さ)
L2 隣接する2つの交点部間距離(線分P2Q2の長さ)
L3 線分P1P2からL1とL2を引いた長さ
L4 交点部の厚み
L5 中央部の平均厚み
R1 側面から観察したときの交点部間距離
R2 交点部間における中央部
C1 L1を半径とする円
C2 L2を半径とする円
D1 P1P2に垂直かつC1の接線を通る繊維径
D2 P1P2に垂直かつC2の接線を通る繊維径
D3 太径部(繊維状物Bの断面の接線が繊維状物Aを通る線分)
D4 太径部(繊維状物B′の断面の接線が繊維状物Aを通る線分)
W1 繊維の横断面の最大径
W2 W1に垂直な方向の最大径
Claims (10)
- 少なくとも集水管と、分離膜と、供給側流路材と、透過側流路材とを備える分離膜エレメントであって、
前記供給側流路材は、前記分離膜の二つの面の間に配置されて供給側流路を形成しており、
前記供給側流路材は、一方向に並んだ、繊維状物Aから構成される複数の繊維状列X、および前記繊維状列Xとは異なる方向に並んだ、繊維状物Bから構成される複数の繊維状列Yとが互いに立体交差して交点を形成したネット形状であり、
前記繊維状物Aおよび前記繊維状物Bの少なくとも一方は、長手方向に沿って太径部と細径部とを有し、
前記繊維状物Aおよび前記繊維状物Bの少なくとも一方は、任意の繊維状列を含む、当該任意の繊維状列の長手方向に沿った縦断面において、前記繊維状列Xおよび前記繊維状列Yの交点部間における中央部が前記太径部に比べて細径の糸で構成されており、
供給側流路面積率が45~65%であり、かつ、
前記供給側流路材の平面から厚み方向に観察したとき、任意の交点と隣り合う交点間の繊維が一方から他方に向かってテーパー状に拡径しているテーパー状繊維である、分離膜エレメント。 - 前記テーパー状繊維のテーパー率が1/20~1/3の範囲である請求項1に記載の分離膜エレメント。
- 前記テーパー状繊維が、原水側から濃縮水側に向かって先細りとなった形状である請求項1または2に記載の分離膜エレメント。
- 前記供給側流路材の剛軟度(m)が0.07m以上0.14m以下である請求項1~3のいずれか1項に記載の分離膜エレメント。
- 前記供給側流路材は、前記供給側流路材の厚みと面積の積で表される総体積Vに対する空隙体積vの割合が90~97%の範囲である請求項1~4のいずれか1項に記載の分離膜エレメント。
- 前記供給側流路材の空隙体積vに対する前記分離膜エレメントの供給側流路体積Fの割合が90%以上である請求項1~5のいずれか1項に記載の分離膜エレメント。
- 前記供給側流路材の原水流れ方向に対して垂直方向の交点部の間隔が3~5mmの範囲である請求項1~6のいずれか1項に記載の分離膜エレメント。
- 前記供給側流路材の原水流れ方向に対して平行方向の交点部の間隔が4~8mmの範囲である請求項1~7のいずれか1項に記載の分離膜エレメント。
- 前記供給側流路材が、前記供給側流路材の任意の繊維状物の長手方向に対して垂直な方向の横断面Zにおいて、前記任意の繊維状物の最大径W1と前記最大径W1に対して垂直な方向の最大径W2が、1.2<W1/W2<3.0の関係を満たす請求項1~8のいずれか1項に記載の分離膜エレメント。
- 前記透過側流路材が、丸編みトリコットである請求項1~9のいずれか1項に記載の分離膜エレメント。
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WO2023048052A1 (ja) * | 2021-09-24 | 2023-03-30 | 東レ株式会社 | 分離膜エレメント |
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