WO2018056090A1 - 分離膜エレメントおよびその運転方法 - Google Patents
分離膜エレメントおよびその運転方法 Download PDFInfo
- Publication number
- WO2018056090A1 WO2018056090A1 PCT/JP2017/032636 JP2017032636W WO2018056090A1 WO 2018056090 A1 WO2018056090 A1 WO 2018056090A1 JP 2017032636 W JP2017032636 W JP 2017032636W WO 2018056090 A1 WO2018056090 A1 WO 2018056090A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- separation membrane
- channel material
- membrane element
- supply
- water
- Prior art date
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Images
Classifications
-
- 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
- B01D63/103—Details relating to membrane envelopes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/025—Reverse osmosis; Hyperfiltration
-
- 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
- B01D63/107—Specific properties of the central tube or the permeate channel
-
- 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
-
- 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
-
- 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
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- 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
- B01D2311/06—Specific process operations in the permeate stream
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2313/00—Details relating to membrane modules or apparatus
- B01D2313/08—Flow guidance means within the module or the apparatus
-
- 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
- B01D2325/20—Specific permeability or cut-off range
Definitions
- the present invention relates to a separation membrane element used for separating components contained in a fluid such as liquid or gas.
- Separation membranes used in separation methods 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 sizes and separation functions. These membranes are used, for example, in the production of drinking water from seawater, brine, and water containing harmful substances, in the production of industrial ultrapure water, and in wastewater treatment and recovery of valuable materials. Depending on the separation component and separation performance to be used.
- separation membrane elements there are various types of separation membrane elements, but when the separation component is water, it is common in that supply water is supplied to one surface of the separation membrane and permeated water is obtained from the other surface.
- the separation membrane element includes a large number of bundled separation membranes so that the membrane area per one separation membrane element is increased, that is, the amount of permeated water obtained per one separation membrane element is increased. Is formed.
- As the separation membrane element various shapes such as a spiral type, a hollow fiber type, a plate-and-frame type, a rotating flat membrane type, and a flat membrane integrated type have been proposed according to applications and purposes.
- spiral separation membrane elements are widely used for reverse osmosis filtration.
- the spiral separation membrane element includes a water collecting pipe and a laminated body wound around the water collecting pipe.
- the laminate includes a supply-side channel material that supplies supply water to the separation membrane surface, a separation membrane that separates components contained in the supply water, and permeate-side water that has passed through the separation membrane and has been separated from the supply water-side fluid. It is formed by laminating a permeate-side channel material for guiding to the water collecting pipe. Since the spiral separation membrane element can apply pressure to the supply water, it is preferably used in that a larger amount of permeated water can be taken out.
- the supply-side flow path material is thick, the flow resistance generated when the spiral separation membrane element is operated is small, and even if the supply-side flow path material is further thinned, the increase in flow resistance is slight, A method has been adopted in which the supply-side channel material is thinned and the amount of separation membrane is increased.
- Patent Document 1 proposes a spiral separation membrane element in which a supply-side channel material having a thickness of 0.08 mm or more and 2 mm or less is filled and a channel material having a low resistance is arranged on the permeation side. ing.
- Patent Document 2 proposes a spiral-type separation membrane element in which the turbulent flow effect on the membrane surface is increased by providing convex portions and grooves on the supply side surface of the separation membrane.
- the separation membrane element is not sufficient from the viewpoint of water production and removability, and there is room for improvement in terms of maintaining the performance of the separation membrane element for a long period of time. It was.
- an object of the present invention is to provide a separation membrane element that is excellent in water formation and removability over a long period of time.
- the present invention comprises the following configurations (1) to (10).
- a separation membrane element comprising a water collecting pipe, a separation membrane comprising a supply side surface and a permeation side surface, a supply side channel material, and a permeation side channel material, wherein the separation membrane, the supply The side channel material and the permeate side channel material are spirally wound around the water collection pipe, and the supply side channel material includes a plurality of fibrous materials intersecting each other,
- the separation membrane has a thickness of 0.15 mm or more and 0.50 mm or less, and the separation water is filtered under the conditions of an operating pressure of 0.41 MPa and a temperature of 25 ° C.
- the feed water is a NaCl solution having a concentration of 200 ppm and a pH 6.5 aqueous solution, and the amount of permeated water when filtered under conditions of an operating pressure of 0.41 MPa and a temperature of 25 ° C.
- the separation membrane element according to (1) which is m 2 / day or more.
- the supply side flow path formed by the supply side flow path material is formed in a direction perpendicular to the longitudinal direction of the water collecting pipe, according to any one of (1) to (4) above. Separation membrane element.
- a method for operating a separation membrane element wherein the separation membrane element according to any one of (1) to (8) above is used to produce 60% or more of the supplied water amount.
- a method for operating a separation membrane element wherein the separation membrane element according to any one of (1) to (8) above is used to produce 40% or less of the supplied amount of water.
- the present invention becomes an element configuration having a high water freshening ability and a high removal ability, and further, hardly soluble salt (scale) and organic matter fouling hardly occur on the membrane surface particularly in the high recovery rate operation by improving the membrane surface linear velocity.
- a separation membrane element excellent in water-repellent property and removability can be obtained for a long time.
- a polymer net is mainly used as a supply-side channel material in order to form a supply-side water channel.
- a separation membrane for example, a stacked type separation membrane is used.
- Laminated separation membranes consist of a separation functional layer made of a crosslinked polymer such as polyamide, a porous resin layer made of a polymer such as polysulfone (porous support layer), polyethylene terephthalate, which are laminated in order from the supply side to the permeation side.
- a substrate such as a nonwoven fabric made of a polymer such as Further, in order to form a flow path of water on the permeate side, a permeate side flow path material is used.
- the separation membrane element has a supply-side channel material 1 sandwiched between separation membranes 2 and a permeation-side channel material 3 is stacked to form a unit, and spirally around the water collection pipe 4.
- the separation membrane element 5 is wound around.
- the separation membrane element 5 includes end plates 92 with holes disposed at the first and second ends thereof and having holes. That is, the supply water 101 supplied from the first end of the separation membrane element 5 is divided into the permeated water 102 and the concentrated water 103 by the separation membrane. The permeated water 102 is taken out from the second end of the separation membrane element 5 through the water collection pipe 4. The concentrated water 103 flows out of the separation membrane element 5 through the hole of the end plate 92 with the hole at the second end.
- the separation membrane element 5B having a different flow of the supply water can be employed.
- the supply side flow path formed by the supply side flow path material is provided in a direction parallel to the longitudinal direction of the water collection pipe 4, whereas in the separation membrane element 5 B, at least the water collection pipe 4 is provided. It is provided in a direction perpendicular to the longitudinal direction.
- the manufacturing method of the separation membrane element 5B is as follows. Specifically, the supply-side channel material 1 is sandwiched between the separation membranes 2, and the permeation-side channel material 3 is laminated to form a set of units, which are wound around the water collection pipe 4 in a spiral shape. Thereafter, edge cutting at both ends is performed, and a sealing plate (corresponding to the first end plate 91) for preventing inflow of supply water from one end is attached, and further, an end plate corresponding to the second end plate 93 is covered.
- a separation membrane element can be obtained by attaching to the other end of the wound body.
- porous member 82 a member having a plurality of holes through which feed water can be passed is used. These holes 821 provided in the porous member 82 may be rephrased as supply water supply ports. As long as the porous member 82 has a plurality of holes, the material, size, thickness, rigidity, and the like are not particularly limited. By adopting a relatively thin member as the porous member 82, the membrane area per unit volume of the separation membrane element can be increased.
- the holes 821 provided in the porous member 82 are shown in a slit shape (straight), but a structure in which a plurality of holes such as a circle, a rectangle, an ellipse, and a triangle are arranged may be used.
- the thickness of the porous member 82 is, for example, preferably 1 mm or less, more preferably 0.5 mm or less, and further preferably 0.2 mm or less.
- the porous member 82 may be a member having flexibility or flexibility that can be deformed so as to follow the outer peripheral shape of the wound body. More specifically, as the porous member 82, a net, a porous film, or the like can be applied. The net and the porous film may be formed in a cylindrical shape so that the wound body can be accommodated therein, or may be long and wound around the wound body.
- the porous member 82 is disposed on the outer peripheral surface of the separation membrane element 5B. By providing the porous member 82 in this manner, holes are provided on the outer peripheral surface of the separation membrane element 5B. It can be said that the “outer peripheral surface” is a portion excluding the first end surface and the second end surface in the entire outer peripheral surface of the separation membrane element 5B. In this embodiment, the porous member 82 is disposed so as to cover almost the entire outer peripheral surface of the wound body.
- the end plate at the first end is the end plate 91 without holes, so that the feed water does not flow into the separation membrane element 5B from the surface of the first end.
- the supply water 101 flows into the gap between the vessel and the separation membrane element 5B.
- the supply water 101 is supplied to the separation membrane 2 from the outer peripheral surface of the separation membrane element 5B through the porous member 82 in a direction perpendicular to the longitudinal direction of the water collecting pipe.
- Supply water 101 supplied in this way is divided into permeated water 102 and concentrated water 103 by the separation membrane.
- the permeated water 102 passes through the water collection pipe 6 and is taken out from the second end of the separation membrane element 5B.
- the concentrated water 103 flows out of the separation membrane element 5B through the hole of the end plate 93 with the second end.
- the separation membrane element in which the supply side flow path formed by the supply side flow path material is provided at least in the direction perpendicular to the longitudinal direction of the water collecting pipe has a width of the separation membrane element.
- the supply-side flow path is provided in a direction parallel to the longitudinal direction of the water collecting pipe.
- a separation membrane element 5C having a different flow of supplied water can be employed.
- the holeless end plate 91 at the first end of the separation membrane element 5B is changed to a holed end plate 94, and the supply water 101 flows from both the outer peripheral surface and the first end of the separation membrane element 5B. Can be taken.
- the separation membrane element 5C can be manufactured in the same procedure as the separation membrane element 5B except that the holeless end plate 91 is changed to the holed end plate 94.
- the separation membrane element 5C is also provided with a supply-side flow path formed by the supply-side flow path material in a direction perpendicular to the longitudinal direction of the water collecting pipe.
- the separation membrane 2 a membrane having separation performance according to the method of use, purpose, and the like is used.
- the separation membrane 2 may be a single layer or a laminated composite membrane including a separation functional layer and a substrate.
- a porous support layer may be further provided between the separation functional layer and the substrate.
- the surface having the separation functional layer is referred to as the supply side surface
- the surface opposite to the surface having the separation functional layer is referred to as the transmission side surface
- the separation is performed in such a state that the supply side surfaces face each other.
- the membrane is called a separation membrane pair.
- the separation function layer may be a layer having both a separation function and a support function, or may have only a separation function.
- the “separation function layer” refers to a layer having at least a separation function.
- a layer containing a polymer selected from the group consisting of cellulose, polyvinylidene fluoride, polyethersulfone and polysulfone as a main component is preferably applied as the separation functional layer.
- a crosslinked polymer is preferably used in terms of easy control of the pore diameter and excellent durability.
- a polyamide separation functional layer obtained by polycondensation of a polyfunctional amine and a polyfunctional acid halide, an organic-inorganic hybrid functional layer, or the like is preferably used because of excellent separation performance of components in the feed water.
- These separation functional layers can be formed by polycondensation of monomers on the porous support layer.
- a separation functional layer containing polyamide as a main component can be formed by interfacial polycondensation of a polyfunctional amine and a polyfunctional acid halide by a known method. More specifically, after applying a polyfunctional amine aqueous solution on the porous support layer and removing the excess polyfunctional amine aqueous solution with an air knife or the like, applying an organic solvent solution containing a polyfunctional acid halide. Thus, polycondensation occurs and a polyamide separation functional layer is formed.
- an aliphatic carboxylic acid having a linear or branched alkyl group and having 5 or more carbon atoms By performing the interfacial polycondensation in the presence of an aliphatic carboxylic acid having a linear or branched alkyl group and having 5 or more carbon atoms, it is possible to precisely control the distribution of terminal functional groups. Thus, both water permeability and removability can be achieved.
- Such an aliphatic carboxylic acid can be added to an aqueous solution of the polyfunctional amine or an organic solvent solution immiscible with water containing the polyfunctional acid halide, or can be impregnated in advance in a porous support membrane. .
- aliphatic carboxylic acid for example, as a linear saturated alkyl carboxylic acid, caproic acid, heptanoic acid, caprylic acid, pelargonic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid or tridecanoic acid is branched.
- Examples of the chain saturated alkylcarboxylic acid include caprylic acid, isobutyric acid, isopentanoic acid, butylacetic acid, 2-ethylheptanoic acid and 3-methylnonanoic acid, and examples of the unsaturated alkylcarboxylic acid include methacrylic acid, trans- Examples include 3-hexenoic acid, cis-2-octenoic acid, or trans-4-nonenoic acid.
- the total carbon number of these aliphatic carboxylic acids is preferably in the range of 5-20, more preferably in the range of 8-15. If the total carbon number is less than 5, the effect of improving the water permeability of the separation functional membrane tends to be small, and if the total carbon number exceeds 20, the boiling point becomes high and it is difficult to remove from the membrane. It tends to be difficult to develop water permeability.
- the water permeability of the membrane is improved by setting the HLB value to 4 or more and 12 or less. And stain resistance are improved at the same time, and further, it is easy to remove from the porous support membrane.
- the HLB value is a value representing the degree of affinity for water-immiscible organic solvents.
- concentration of the aliphatic carboxylic acid in the organic solvent solution can be appropriately determined depending on the aliphatic carboxylic acid to be added. Specifically, it is preferably in the range of 0.03 to 30% by mass, More preferably, it is in the range of 06 to 10% by mass.
- the porous support layer is a layer that supports the separation functional layer, and can be rephrased as a porous resin layer when the material is a resin.
- the material used for the porous support layer and its shape are not particularly limited, but may be formed on the substrate with a porous resin, for example.
- a porous resin for example.
- polysulfone, cellulose acetate, polyvinyl chloride, epoxy resin or a mixture and laminate of them is used, and polysulfone with high chemical, mechanical and thermal stability and easy to control pore size. Is preferably used.
- the porous support layer is formed by casting an N, N-dimethylformamide (DMF) solution of the above polysulfone onto a substrate (for example, a densely woven polyester nonwoven fabric) described later to a certain thickness, It can be manufactured by wet coagulation with.
- DMF N, N-dimethylformamide
- the porous support layer is “Office of Saleen Water Research and Development Progress Report” No. 359 (1968).
- the polymer concentration, the temperature of the solvent, and the poor solvent can be adjusted.
- the separation membrane may have a substrate.
- the substrate it is preferable to use a fibrous substrate in terms of strength and fluid permeability.
- a long fiber nonwoven fabric and a short fiber nonwoven fabric can be preferably used.
- the separation membrane filled in the separation membrane element of the present invention was cut out to 47 cm 2 , and the feed water was a saline solution having a concentration of 200 ppm and a pH 6.5 aqueous solution, an operating pressure of 0.41 MPa, a temperature of 25 ° C., and a recovery rate of 1%.
- the pure water permeability coefficient was A (m / second / MPa) and the solute permeability coefficient was B (m / second), A 3
- the separation membrane has high performance (high water permeability and high removal).
- the higher the performance of the separation membrane the greater the amount of supplied water and the membrane surface salt concentration, and the corresponding flow resistance of the flow path.
- the separation membrane element of the present invention can stably exhibit higher performance than the conventional separation membrane element even when a high-performance separation membrane is mounted. .
- the separation membrane element is provided with a supply-side flow path member disposed so as to face the supply-side surface of the separation membrane.
- the supply-side flow path material only needs to be formed so as to form a flow path for supplying the supply water to the separation membrane 2, and is provided so as to disturb the flow of the supply water in order to suppress the concentration polarization of the supply water. It is preferable that
- the supply side channel material is a member having a continuous shape such as a knitted fabric, a woven fabric or a net.
- a net is preferably used from the viewpoint of securing the flow path of the supply water and suppressing concentration polarization.
- the net in the present application is a structure having a mesh shape in which a plurality of fibrous objects (constituent fibers) intersecting each other are heat-sealed, and is a longitudinal fiber shape discharged from a hole provided in an extrusion die. It is manufactured by adhering a resin in a molten state and a resin in a lateral direction in a molten state, and then cooling and solidifying it.
- the supply-side channel material includes a fibrous array A composed of a plurality of fibrous objects A11 aligned in one direction, and a plurality of fibrous structures aligned in a direction different from the fibrous array A. It consists of the fibrous row
- the supply water flow path to the membrane surface becomes narrower. It is preferably not more than °, more preferably not less than 75 ° and not more than 105 °.
- the thickness of the supply-side channel material substantially corresponds to the intersection thickness of the fibrous material A and the fibrous material B in FIG. If the thickness of the supply-side channel material is reduced, the linear velocity of the supplied water is increased and the flow of the membrane surface is disturbed, so that the concentration polarization layer is reduced and the separation performance of the separation membrane element is improved.
- the thinner the channel material the more separation membranes that can be filled in the separation membrane element, leading to an improvement in the amount of water produced by the separation membrane element.
- the thickness of the supply-side channel material needs to be 0.15 mm or more and 0.50 mm or less, and preferably 0.28 mm or more and 0.35 mm or less.
- the thickness of the supply-side channel material is the average value of the values measured with a precision thickness gauge or the like for the intersection thickness of 30 fibrous materials A and fibrous materials B selected at random.
- the intersection thicknesses of the fibrous material A and the fibrous material B are both The average thickness of the supply-side channel material is preferably 0.9 times or more and 1.1 times or less.
- the constituent fiber diameter of the fibrous material can be measured by observing with a commercially available microscope.
- the constituent fiber diameter of the fibrous object A11 and the constituent fiber diameter of the fibrous object B12 shown in FIG. 4 are the widths c and d of the images obtained by projecting the respective fibrous objects on a plane parallel to the surface direction of the separation membrane.
- the constituent fiber diameter of the supply-side channel material shown in FIG. 4 is smaller, the region where the supply water is stagnated decreases, but the rigidity becomes lower. On the other hand, when the constituent fiber diameter is large, the rigidity is increased, but the region where the feed water is stagnated increases. From these balances, the constituent fiber diameter of the supply-side channel material is preferably 0.07 mm or more and 0.25 mm or less, and more preferably 0.14 mm or more and 0.18 mm or less.
- the constituent fiber diameter of the fibrous object A and the constituent fiber diameter of the fibrous object B may be the same or different.
- the intersection distance of the supply-side channel material is 0.5 mm or more and 10 mm or less.
- the supply-side channel material is sandwiched between the separation membranes, and the permeation-side channel material is laminated to form a set of units that are wrapped around the water collection pipe while being pressurized spirally.
- the distance between the intersections of the supply-side flow path members is 1.5 mm or less, the force with which the intersections of the nets are pressed against the separation membrane can be dispersed, and damage to the separation membrane can be reduced.
- the hardness of the feed water is high and the water-making property and removability of the separation membrane are high, especially during the high recovery rate operation, a region where the feed water stagnates mainly at the intersection position of the feed-side flow path material, Since the salt concentration increases and the inorganic scale adheres, it is effective to suppress the adhesion of the inorganic scale to the film surface when the supply side flow path material has an intersection distance of 8 mm or more.
- the upper limit of the intersection distance is preferably 10 mm in order to ensure the winding hardness of the element and reduce an excessive load on the film.
- intersection density is the number of intersections of the fibrous material A and the fibrous material B that constitute the supply-side channel material existing per unit area. For example, it can be obtained by observing the supply-side channel material from the height direction with respect to the plane direction and measuring the number of intersection points per 100 mm 2 selected at random.
- the flow rate of the supplied water can be moderated.
- the separation membrane has a high water-producing ability and the amount of water supplied to the separation membrane element is large, the resistance of the supply-side flow path can be reduced, and a separation membrane element excellent in water formation can be obtained.
- intersection density is 3 pieces / 100 mm 2 or less, particularly in the case where the hardness of the supply water is high and the high recovery rate operation is performed, there is a region where the supply water stagnates at the intersection position of the supply side channel material. This is effective in suppressing adhesion of inorganic scale to the film surface.
- Cross-sectional shape of fibrous material Since it is important to increase the degree of turbulent flow around the separation membrane surface in the supply-side flow path, it is also possible to use an irregularly shaped fibrous material having a cross section that is not circular or elliptical.
- the “irregular” cross section includes all non-circular shapes.
- a Y-shaped, T-shaped, X hour-shaped, star-shaped, gear-shaped, etc. The shape to include is mentioned. Due to the presence of the recesses in the fibrous material, there will be a mixture of areas where the feed water is easy to flow and areas where it is difficult to flow around the supply side flow material. .
- a fibrous material having a modified cross section is a technique well known in the art.
- a fibrous material having various modified cross sections can be formed by changing the shape of the extrusion die as necessary. is there.
- the material of the supply-side channel material is not particularly limited, but a thermoplastic resin is preferable from the viewpoint of moldability, and polyethylene and polypropylene are particularly preferable because they hardly damage the surface of the separation membrane and are inexpensive.
- the permeation side flow path material is disposed on the permeation side surface of the separation membrane.
- a projection is formed by forming a projection on a film or a nonwoven fabric, and the projection is arranged and fixed on a sheet imparted with a channel material function or a porous sheet such as a nonwoven fabric. The sheet
- the permeation-side flow path material has a cross-sectional area ratio of 0.4 or more and 0.75 or less in that the flow resistance of the permeation-side flow path is reduced and the flow path is stably formed even under pressure filtration. It is preferable.
- the cross-sectional area ratio of the permeate side channel material will be described.
- FIG. 5 as an example, a sheet-shaped permeation-side flow path material is shown, but when the permeation-side flow path material is filled in the separation membrane element, the permeation-side flow path is along a direction parallel to the longitudinal direction of the water collecting pipe.
- the ratio of the cross-sectional area S of the permeation-side flow path material occupied between the center of one convex part and the center of the adjacent convex part is the cross-sectional area ratio.
- the permeate-side channel material is directly fixed to the permeate-side surface of the separation membrane as shown in FIG.
- there are a plurality of permeation-side channel materials and the cross-sectional area of the permeation-side channel material occupying between the center of the convex portion and the center of the adjacent convex portion is two (S1 and S2).
- the cross-sectional area S corresponds to the sum of S1 and S2.
- the permeation side channel material having a cross-sectional area ratio of 0.4 or more and 0.75 or less By disposing the permeation side channel material having a cross-sectional area ratio of 0.4 or more and 0.75 or less in the separation membrane element of the present invention, the flow resistance of the permeation side channel can be reduced. As a result, the unit membrane Water permeability per area can be improved.
- the improvement in water permeability per unit membrane area means that the water permeability of the entire separation membrane element is improved, and includes a channel material having a large permeation-side flow resistance when operating at a constant recovery rate.
- the separation membrane element the effect of increasing the flow rate and linear velocity of the feed water is born, and by increasing the membrane surface turbulence effect, concentration polarization is suppressed, and the separation membrane and the supply-side channel material can be used during long-term operation. Contaminant adhesion can be suppressed, and the water-making property and removability of the separation membrane element can be maintained for a long time.
- the thickness H0 of the permeate side channel material in FIG. 7 is preferably 0.1 mm or more and 1 mm.
- Various methods such as an electromagnetic method, an ultrasonic method, a magnetic method, and a light transmission method are commercially available for measuring the thickness, but any method may be used as long as it is a non-contact type. Measurements are made at 10 locations at random and the average value is taken as the thickness of the permeate-side channel material.
- the thickness of the permeate side channel material is 0.1 mm or more, it has strength as a permeate side channel material and can be handled without causing crushing or tearing of the permeate side channel material even when stress is applied. it can.
- the thickness of the permeate-side channel material is 1 mm or less, the number of separation membranes and permeate-side channel materials that can be filled in the separation membrane element is increased without impairing the surrounding property of the water collecting pipe. Can do.
- the thickness H0 of the permeate-side channel material is the convex portion of the permeate-side channel material described later. It is the same as the height H1.
- the height H1 of the convex portion of the permeate-side channel material in FIG. 7 is preferably 0.05 mm or more and 0.8 mm or less, and the groove width D is preferably 0.02 mm or more and 0.8 mm or less.
- the height H1 and the groove width D of the protrusions can be measured by observing the cross section of the permeate-side channel material with a commercially available microscope at 30 points selected at random, and can be calculated as an average value thereof. it can.
- the space formed by the height H1 of the convex portion, the groove width D, and the laminated separation membrane becomes a permeate-side flow path, and the pressure filtration is performed because the height H1 and the groove width D of the convex portion are in the above ranges. It is possible to obtain a separation membrane element excellent in pressure resistance and water-forming property while reducing flow resistance while suppressing membrane dropping.
- the groove length E can be set similarly to the groove width D. .
- the width W of the convex portion of the permeate-side channel material in FIG. 7 is preferably 0.1 mm or more, and more preferably 0.3 mm or more.
- the width W is preferably 1 mm or less, more preferably 0.7 mm or less. When the width W is 1 mm or less, it is possible to sufficiently secure the permeation side flow path.
- the width W of the convex portion 6 is measured as follows. First, in one cross section perpendicular to the first direction, the average value of the maximum width and the minimum width of one convex portion 6 is calculated. That is, in the convex part 6 whose upper part is thin and whose lower part is thick as shown in FIG. 9, the width of the lower part and the upper part of the channel material are measured, and the average value is calculated. By calculating such an average value in at least 30 cross sections and calculating an arithmetic average thereof, the width W per film can be calculated.
- transmission side flow-path material is the width W. It can be set similarly.
- the sheet constituting the permeation-side channel material a porous film or a nonwoven fabric can be used, and in the case of the nonwoven fabric in particular, the space that becomes the channel formed by the fibers constituting the nonwoven fabric becomes wider. It is preferable because water easily flows and, as a result, the water forming property of the separation membrane element is improved.
- the polymer that is the material of the permeate-side channel material is not particularly limited as long as it retains the shape as the permeate-side channel material and has little elution of components into the permeated water.
- the sheet is composed of a plurality of fibers
- fibers having a polypropylene / polyethylene core-sheath structure may be used.
- the transmission side flow channel material itself is shaped into a corrugated plate shape, rectangular wave shape, triangular wave shape, etc., or one surface of the transmission side flow channel material is flat and the other surface is processed to be uneven. Further, it may be formed by laminating other members on the surface of the permeate-side flow path material in an uneven shape.
- the convex portions forming the flow path may have a dot shape as shown in FIG.
- FIG. 8 illustrates a cylindrical projection having a circular cross section (a plane parallel to the sheet plane)
- the cross sectional shape is not particularly limited, such as a polygon or an ellipse.
- the convex part of a different cross section may be mixed.
- corrugated shape which has a groove
- the groove is preferably continuous in a direction perpendicular to the longitudinal direction of the water collecting pipe in order to introduce permeate into the water collecting pipe at the shortest distance.
- the cross-sectional shape in a direction perpendicular to the winding direction may be a trapezoidal wall-like object having a change in width, an elliptical column, an elliptical cone, a quadrangular pyramid, or a hemispherical shape.
- the separation membrane element of the present invention can be applied to a water treatment system such as an RO water purifier.
- a water treatment system such as an RO water purifier.
- a separation membrane with excellent water production and desalination capacity is installed and operation is performed with a high recovery rate (percentage of permeated water relative to the amount of supplied water)
- the amount of organic foulant supplied to the membrane surface and the inorganic scale As the amount increases, the fouling associated therewith, the effective pressure of the separation membrane element decreases due to the increase in osmotic pressure, and the desalination rate and the water formation of the separation membrane element tend to decrease.
- the recovery rate is set to 60% or more. Even if it is operated for a long time, it has excellent fresh water generation and desalination capabilities.
- the thickness of the intersection of the mesh-like supply side channel material (net) composed of the fibrous material A and the fibrous material B was measured at 30 points using Mitsutoyo Corporation's Thickness Gauge (Part No. 547-315), and the average The value was taken as the thickness of the supply-side channel material.
- the surface of the polysulfone layer of the porous support membrane was immersed in a 2.2% by mass aqueous solution of m-PDA for 2 minutes and then slowly pulled up in the vertical direction. Furthermore, the excess aqueous solution was removed from the surface of the support film by blowing nitrogen from the air nozzle.
- separation membrane a A 15.7% by weight DMF solution of polysulfone was cast on a polyester nonwoven fabric (air permeability 0.5 to 1 cc / cm 2 / sec) to a thickness of 200 ⁇ m at room temperature (25 ° C.), and immediately immersed in pure water.
- a microporous support membrane (thickness: 210 to 215 ⁇ m) was produced by leaving it for a minute.
- the obtained microporous support membrane was immersed in a 1.8% by mass aqueous solution of m-PDA for 2 minutes, the support membrane was slowly pulled up in the vertical direction, and nitrogen was blown from an air nozzle to remove excess from the surface of the support membrane.
- an n-decane solution at 25 ° C. containing 0.065% by mass of TMC and 0.1% by mass of undecanoic acid was applied so that the surface was completely wetted, and then allowed to stand for 1 minute.
- the membrane was held vertically for 1 minute and drained.
- separation membrane b This separation membrane was designated as separation membrane b.
- separation membrane c A 15.7% by weight DMF solution of polysulfone was cast on a polyester nonwoven fabric (air permeability 0.5 to 1 cc / cm 2 / sec) to a thickness of 200 ⁇ m at room temperature (25 ° C.), and immediately immersed in pure water. A microporous support membrane (thickness: 210 to 215 ⁇ m) was produced by leaving it for a minute.
- the obtained microporous support membrane was immersed in a 1.8% by mass aqueous solution of m-PDA for 2 minutes, the support membrane was slowly pulled up in the vertical direction, and nitrogen was blown from an air nozzle to remove excess from the surface of the support membrane.
- an n-decane solution at 25 ° C. containing 0.065% by mass of TMC and 0.1% by mass of undecanoic acid was applied so that the surface was completely wetted, and further 10 seconds later, 1% by mass of diethylene glycol dimethyl ether The n-decane solution was applied so that the surface was completely wet and allowed to stand for 1 minute.
- the membrane was held vertically for 1 minute and drained. Thereafter, it was washed with hot water at 80 ° C. for 2 minutes to obtain a composite separation membrane roll.
- This separation membrane was designated as a separation membrane c.
- the surface of the polysulfone layer of the porous support membrane was immersed in a 3.0% by mass aqueous solution of m-PDA for 2 minutes, and then slowly pulled up in the vertical direction. Furthermore, the excess aqueous solution was removed from the surface of the support film by blowing nitrogen from the air nozzle.
- Separation membrane f was obtained by changing the membrane surface temperature at the time of contact between amine and trimesic acid chloride during preparation of the separation membrane to 40 ° C.
- Separatation membrane flux The separation membrane was cut out to 47 cm 2, and the conditions of an operating pressure of 0.41 MPa, a temperature of 25 ° C., and a recovery rate of 1% or less were used in the membrane evaluation cell using a 200 ppm concentration saline solution and a pH 6.5 NaCl aqueous solution as the feed water. After operating for 15 minutes, sampling was performed for 1 minute, and the amount of water per day was defined as a separation membrane flux (m 3 / m 2 / day).
- Pure water permeability coefficient (m 3 / m 2 / sec / Pa) (membrane permeation flux of solution) / (pressure difference on both sides of membrane ⁇ osmotic pressure difference on both sides of membrane ⁇ solute reflection coefficient) (a)
- the solute reflection coefficient can be obtained by the following method. First, the following equation is known as a transport equation of the reverse osmosis method based on non-equilibrium thermodynamics.
- Jv is the membrane permeation flux of the solution (m 3 / m 2 / s)
- Lp is the pure water permeability coefficient (m 3 / m 2 / s / Pa)
- ⁇ P is the pressure difference (Pa) on both sides of the membrane
- ⁇ is the solute reflection coefficient
- ⁇ is the osmotic pressure difference (Pa) on both sides of the membrane
- Js is the solute permeability through the membrane (mol / m 2 / s)
- P is the solute permeability coefficient (m / s)
- Cm is the solute membrane.
- the surface concentration (mol / m 3 ), Cp is the permeate concentration (mol / m 3 ), and C is the concentration on both sides of the membrane (mol / m 3 ).
- the average concentration C on both sides of the membrane has no substantial meaning when the concentration difference between the two sides is very large as in a reverse osmosis membrane. Therefore, the following formula obtained by integrating the formula (a) with respect to the film thickness is often used.
- R ⁇ (1-F) / (1- ⁇ F) (d)
- F exp ⁇ -(1- ⁇ ) Jv / P ⁇ (e)
- R 1-Cp / Cm (f)
- Lp Lp can be calculated from the equation (b)
- R is measured by changing Jv in various ways
- R and 1 / Jv are plotted against the equations (d) and (e).
- P and ⁇ can be obtained simultaneously by curve fitting.
- equation (g) is materialized about the desalination rate R of P and a separation membrane.
- R 100 ⁇ Jv / (Jv + P)
- (g) Water generation capacity of separation membrane element
- the separation membrane element was evaluated based on the following three evaluation conditions. (Condition 1) Saline solution having a concentration of 200 ppm and pH 6.5 aqueous solution was used as the feed water, and the sample was sampled for 1 minute after operating for 15 minutes under the conditions of an operating pressure of 0.41 MPa and a temperature of 25 ° C. The water permeability was expressed as the amount of water produced (GPD (gallon / day)).
- Desalination rate (%) 100 ⁇ ⁇ 1- (TDS concentration in permeated water / TDS concentration in feed water) ⁇ (Preparation of transmission side channel material tricot with weft knitting)
- the weft knitted fabric is made of multi-filament yarn (48 filaments, 110 dtex) made by blending polyethylene terephthalate filaments (melting point: 255 ° C) with polyethylene terephthalate-based low melting point polyester filaments (melting point: 235 ° C).
- the weft knitting structure gauge (the number of needles between unit lengths of the knitting machine)) was knitted, heat set at 245 ° C., and then calendered to produce a permeate-side channel material tricot.
- the permeate side channel material is indicated as permeate side channel material A.
- the envelope is perpendicular to the longitudinal direction of the water collection pipe when the backup roll is adjusted to 20 ° C. and used as a separation membrane element
- a highly crystalline PP MFR 1000 g / 10 min, melting point 161 linearly or discontinuously so as to be perpendicular to the longitudinal direction of the water collecting pipe from the inner end to the outer end in the winding direction.
- the nonwoven fabric had a thickness of 0.07 mm, a weight per unit area of 35 g / m 2 , and an embossed pattern (a circle with a diameter of 1 mm, a lattice with a pitch of 5 mm).
- the permeate side channel material is indicated as permeate side channel material B.
- Imprint processing and CO2 laser processing were performed on an unstretched polypropylene film (Torephane (registered trademark) manufactured by Toray Industries, Inc.) to obtain a permeate-side channel material having through holes.
- an unstretched polypropylene film was sandwiched between metal molds having grooves formed by cutting, held at 140 ° C./2 minutes / 15 MPa, cooled at 40 ° C., and taken out from the mold.
- a through hole was obtained by laser processing the concave and convex portions on the concave and convex portions from the non-concave surface of the concave and convex imprint sheet.
- the through holes were provided in each groove with a pitch of 2 mm.
- the permeation side channel material is indicated as permeation side channel material C.
- the separation membrane element that had been evaluated in (Condition 3) and reached a total water production of 3000 L was disassembled, and the membrane surface deposit was extracted with a 1 wt% nitric acid aqueous solution. Measure the total adsorption amount (g) of inorganic components (calcium, magnesium, barium) using an inductively coupled plasma emission spectrometer) and calculate the inorganic scale adhesion amount (g / m 2 ) from the membrane area of the separation membrane element did.
- Total amount of deposits The separation membrane element that had been evaluated in (Condition 3) and reached a total water production of 3000 L was disassembled, and the adhering matter adhering to the membrane surface was collected with a rubber scraper, and then dried at 120 ° C. for 2 hours. The mass was measured, and the total amount of deposits (g / m 2 ) was calculated from the membrane area of the separation membrane element. (Amount of organic fouling attached) The difference between the total deposit amount and the inorganic scale deposit amount was calculated as the organic fouling deposit amount (g / m 2 ).
- the thickness of the permeate side channel material and the height of the convex portion were measured with a high precision shape measurement system KS-1100 manufactured by Keyence Corporation. Specifically, an average height difference was analyzed from a measurement result of 5 cm ⁇ 5 cm using a high precision shape measurement system KS-1100 manufactured by Keyence Corporation. Thirty locations with a height difference of 10 ⁇ m or more were measured, and the average value was defined as the height of the convex portion.
- Example 1 The separation membrane a obtained by the above-mentioned production method is cut and processed, and a polypropylene net (thickness: 300 ⁇ m, intersection distance: 8 mm, fiber diameter: 0.15 mm, inclination angle: 90 °) shown in Table 2 is supplied on the supply side flow path The leaves were sandwiched and folded to produce a leaf.
- a permeation side flow path material B (cross-sectional area ratio: 0.43) shown in Table 2 was laminated as a permeation side flow path material on the permeation side surface of the obtained leaf, and a leaf adhesive was applied.
- the separation membrane pair is arranged so that the length of the side perpendicular to the longitudinal direction of the water collection pipe is longer than the width of the separation membrane element, and the ABS (acrylonitrile-butadiene-styrene) water collection pipe (width) : 298mm, diameter: 17mm, number of holes 8 holes x 2 straight lines) spirally wound around the outer peripheral surface of the wound body, continuously extruded into a cylindrical shape (thickness: 0.7mm, pitch: 5mm) ⁇ 5 mm, fiber diameter: 350 ⁇ m, projected area ratio: 0.13).
- a sealing plate (corresponding to the first end plate 91) for preventing inflow of supply water from one end was attached.
- the supply water supply port was provided only on the outer peripheral surface of the separation membrane element.
- a separation membrane element having a diameter of 1.8 inches is prepared by attaching an end plate corresponding to the second end plate 92 to the other end of the covered envelope and providing a concentrated fluid outlet at the other end of the separation membrane element. did.
- the obtained separation membrane element was put in a pressure vessel, and the performance was evaluated under the above-mentioned conditions.
- the separation membrane element after evaluation in (Condition 3) was disassembled, and the amount of inorganic scale, the total amount of deposit, and the amount of organic fouling were measured. The results are shown in Table 3.
- the effective membrane area in Table 1 is a region in the separation membrane leaf where the separation function is not deactivated by the leaf adhesive.
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Abstract
Description
(1) 集水管と、供給側の面と透過側の面とを備える分離膜と、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、上記分離膜、供給側流路材および透過側流路材は上記集水管の周りにスパイラル状に巻囲され、上記供給側流路材は、互いに交差する複数の繊維状物を備え、上記供給側流路材の厚みが0.15mm以上0.50mm以下であり、上記分離膜は、供給水を濃度200ppmの食塩水、pH6.5のNaCl水溶液とし、運転圧力0.41MPa、温度25℃の条件下でろ過した際の溶液透過係数をA(m/秒/MPa)、溶質透過係数をB(m/秒)とした際に、A3/B(m2/秒2/MPa3)の値が8.0×10-8以上である、分離膜エレメント。
(2) 上記分離膜は、供給水を濃度200ppmの食塩水、pH6.5のNaCl水溶液とし、運転圧力0.41MPa、温度25℃の条件下でろ過した際の透過水量が1.5m3/m2/日以上である、上記(1)に記載の分離膜エレメント。
(3) 上記供給側流路材の交点密度が3個/100mm2以下である、上記(1)又は(2)に記載の分離膜エレメント。
(4) 上記供給側流路材の交点密度が15個/100mm2以上210個/100mm2以下である、上記(1)又は(2)に記載の分離膜エレメント。
(5) 上記供給側流路材により形成される供給側流路が、上記集水管の長手方向に対して垂直方向に形成されている、上記(1)~(4)のいずれかに記載の分離膜エレメント。
(6) 上記透過側流路材は、複数の突起物が形成されたシート又は複数の突起物が固着されたシートである、上記(1)~(5)のいずれかに記載の分離膜エレメント。
(7) 上記突起物が、上記集水管の長手方向に対して垂直方向に連続している、上記(6)に記載の分離膜エレメント。
(8) 上記透過側流路材の横断面が複数の透過側流路を形成し、かつ、上記透過側流路材の横断面積比が0.4以上0.75以下である、上記(1)~(7)のいずれかに記載の分離膜エレメント。
(9) 上記(1)~(8)のいずれかに記載の分離膜エレメントを用いて、供給された水量の60%以上を造水する、分離膜エレメントの運転方法。
(10) 上記(1)~(8)のいずれかに記載の分離膜エレメントを用いて、供給された水量の40%以下を造水する、分離膜エレメントの運転方法。
分離膜エレメントでは、供給側の水の流路を形成させるために、供給側流路材として、主に高分子製のネットが使用される。また、分離膜としては例えば、積層型の分離膜が用いられる。積層型の分離膜は、供給側から透過側に順に積層された、ポリアミドなどの架橋高分子からなる分離機能層、ポリスルホンなどの高分子からなる多孔性樹脂層(多孔性支持層)、ポリエチレンテレフタレートなどの高分子からなる不織布などの基材を備えている。また、透過側の水の流路を形成させるために、透過側流路材が用いられる。分離膜エレメントは、図1に示すように、供給側流路材1を分離膜2で挟み込み、透過側流路材3を積層させて一組のユニットとし、集水管4の周囲にスパイラル状に巻囲して分離膜エレメント5としている。
(概要)
分離膜2としては、使用方法、目的などに応じた分離性能を有する膜が用いられる。分離膜2は、単一層であってもよいし、分離機能層と基材とを備える積層型の複合膜であってもよい。また、複合膜においては、分離機能層と基材との間に、さらに多孔性支持層があってもよい。
分離機能層は、分離機能および支持機能の両方を有する層であってもよいし、分離機能のみを備えていてもよい。なお、「分離機能層」とは、少なくとも分離機能を備える層を指す。
=20×(親水部の式量の総和)/(分子量)
上記有機溶媒溶液における脂肪族カルボン酸の濃度は、添加する脂肪族カルボン酸によって適宜決定することができるが、具体的には、0.03~30質量%の範囲内にあると好ましく、0.06~10質量%の範囲内であるとさらに好ましい。
多孔性支持層は、分離機能層を支持する層であり、材料が樹脂の場合多孔性樹脂層とも言い換えることができる。
分離膜の強度、寸法安定性などの観点から、分離膜は基材を有してもよい。基材としては、強度、流体透過性の点で繊維状の基材を用いることが好ましい。
本発明の分離膜エレメントに充填される分離膜は、47cm2に切り出し、供給水を濃度200ppmの食塩水、pH6.5のNaCl水溶液とし、運転圧力0.41MPa、温度25℃、回収率1%以下の条件下で15分間運転した後に1分間のサンプリングを行った時に、純水透過係数をA(m/秒/MPa)、溶質透過係数をB(m/秒)とした際に、A3/B(m2/秒2/MPa3)の値が8.0×10-8以上を示す分離膜である。これは、分離膜が高性能(高透水かつ高除去)であることを示しており、分離膜が高性能であるほど、供給水量と膜面塩濃度は増加し、それに伴い流路の流動抵抗と膜面ファウリングリスクが増大するが、本発明の分離膜エレメントでは、高性能の分離膜を搭載しても、従来の分離膜エレメントよりも高い性能を安定して発現させることが可能となる。
(概要)
分離膜エレメントは、分離膜の供給側の面に対向するように配置された供給側流路材を備えている。供給側流路材は、分離膜2に供給水を供給する流路を形成するように形成されていればよく、供給水の濃度分極を抑制するために、供給水の流れを乱すように設けられていることが好ましい。
図4に示した供給側流路材の繊維状物(構成繊維)の傾斜角e又はfは、0°又は180°に近いほど、膜面への供給水流路が狭まるため、60°以上120°以下であることが好ましく、75°以上105°以下がより好ましい。
(厚み)
供給側流路材の厚みとは、図4においては実質的に繊維状物Aおよび繊維状物Bの交点厚みに相当する。供給側流路材の厚みは、薄くすれば、供給水の線速が大きくなり膜面の流れが乱れるので、濃度分極層が薄くなり、分離膜エレメントの分離性能が向上する。また流路材を薄くするほど分離膜エレメントに充填できる分離膜が増えるため、分離膜エレメントの造水量向上につながる。しかし、あまり供給側流路材の厚みを過度に薄くすると、供給水中の不純物や、微生物などのファウラントが供給側の流路を閉塞する傾向がある。その結果、分離膜エレメントの造水性が低下したり、分離膜エレメントの流動抵抗が大きくなり、供給水を供給するポンプの必要動力が大きくなるため電力費が高くなったり、分離膜エレメントが破損するといった問題が生じるため好ましくない。そこで、供給側流路材の厚みは、0.15mm以上0.50mm以下である必要があり、好ましくは0.28mm以上0.35mm以下である。
(繊維状物の構成繊維径)
繊維状物の構成繊維径は、市販のマイクロスコープなどで観察して測定することができる。図4に示した繊維状物A11の構成繊維径と繊維状物B12の構成繊維径は、それぞれの繊維状物を分離膜の面方向に平行な平面に投影した像の幅c、dをそれぞれ、無作為に選択した30箇所に関して測定を行なった平均値とする。図4に示した供給側流路材の構成繊維径は、小さいほど供給水が澱む領域が減るが、剛性は低くなる。一方で構成繊維径が大きいと、剛性は高くなるが、供給水が澱む領域が増える。それらのバランスから、供給側流路材の構成繊維径は、0.07mm以上0.25mm以下であることが好ましく、0.14mm以上0.18mm以下がより好ましい。なお繊維状物Aの構成繊維径と繊維状物Bの構成繊維径とは、同じであっても、異なっていても構わない。
(繊維状物の交点間隔)
供給側流路材の交点間隔は、前述した繊維状物Aと繊維状物Bとの構成繊維径がいずれも同一の条件で比較すると、その間隔が広いほど供給水の流速は遅くなり、圧力損失は小さくなる。一方で、交点間隔が狭いほど供給水の流速は速くなり、圧力損失は大きくなる。
(交点密度)
交点密度とは、単位面積当たりに存在する供給側流路材を構成する繊維状物Aおよび繊維状物Bの交点数のことである。例えば、供給側流路材を平面方向に対して高さ方向から観察し、無作為に選択した100mm2当たりに存在する交点数を測定することで求めることができる。
(繊維状物の断面形状)
供給側流路においては、分離膜表面周辺の乱流の程度を増すことが重要であるため、断面が円形や楕円形でなく、異形の繊維状物を用いることも可能である。「異形」の断面とは、非円形の全ての形状を包含するものであり、例えば多角形の他にY字型、T字型、X時型、星型、歯車型などの断面に凹部を含む形状が挙げられる。繊維状物に凹部が存在することで、供給側流材の周辺で供給水の流れやすい領域と流れにくい領域が混在することになり、その差により流れに渦が発生して乱流へとなる。
(材料)
供給側流路材の材料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。
(概要)
本発明の分離膜エレメントには、分離膜の透過側面に透過側流路材が配置される。本発明では、透過側流路材として、フィルムや不織布を凹凸加工して突起物を形成し、流路材機能を付与したシートや、不織布のような多孔性シート上に突起物を配置し固着したシートなどを用いることができる。
透過側流路材は、透過側流路の流動抵抗を低減し、かつ加圧ろ過下においても流路を安定に形成させる点では、その横断面積比が0.4以上0.75以下であることが好ましい。ここで、透過側流路材の横断面積比について説明する。図5では一例として、シート状の透過側流路材について示しているが、透過側流路材を分離膜エレメントに充填した際、集水管の長手方向と平行な方向に沿って透過側流路材の凸部を通るように切断し、その断面について、一の凸部の中心と隣接する凸部の中心の距離P(ピッチともいう)と透過側流路材の高さH0の積に対する、一の凸部の中心と隣接する凸部の中心との間に占める透過側流路材の横断面積Sとの比が横断面積比である。
図7における透過側流路材の厚みH0は、0.1mm以上1mmであることが好ましい。厚みの測定は、電磁式、超音波式、磁力式、光透過式など様々な方式のフィルム膜厚測定器が市販されているが、非接触のものであればいずれの方式でも構わない。ランダムに10箇所で測定を行いその平均値を透過側流路材の厚みとする。透過側流路材の厚みが0.1mm以上であることで、透過側流路材としての強度を備え、応力が負荷されても透過側流路材の潰れや破れを引き起こすこと無く取り扱うことができる。また、透過側流路材の厚みが1mm以下であることで、集水管への巻囲性を損なうことなく、分離膜エレメント内に充填できる分離膜や透過側流路材の数を増加させることができる。
図7における透過側流路材の凸部の高さH1は、0.05mm以上0.8mm以下であることが好ましく、溝幅Dは0.02mm以上0.8mm以下であることが好ましい。凸部の高さH1や溝幅Dは、無作為に選択した30箇所について透過側流路材の横断面を市販のマイクロスコープなどで観察することで測定し、その平均値として算出することができる。
図7における透過側流路材の凸部の幅Wは、好ましくは0.1mm以上であり、より好ましくは0.3mm以上である。幅Wが0.1mm以上であることで、分離膜エレメントの運転時透過側流路材に圧力がかかっても、凸部の形状を保持することができ透過側流路が安定的に形成される。幅Wは、好ましくは1mm以下であり、より好ましくは0.7mm以下である。幅Wが1mm以下であることで、透過側流路を十分確保することができる。
透過側流路材を構成するシートとしては、多孔性フィルムや不織布などを用いることができ、特に不織布の場合では、不織布を構成する繊維同士で形成された流路となる空間が広くなるため、水が流動しやすく、その結果、分離膜エレメントの造水性が向上するため好ましい。
透過側流路材の両面に分離膜が配置された際、凸部と隣接する凸部の空間は、透過水の流路となる。流路は、透過側流路材自体が波板状、矩形波状、三角波状などに賦形加工されていたり、透過側流路材の一面が平坦で他の表面が凹凸状に加工されていたり、透過側流路材表面に他の部材が凹凸形状に積層されることによって形成されたものであってもよい。
本発明の分離膜エレメントに適用する透過側流路材は、流路を形成する凸部が、図8に示すようなドット状でも良い。ドットの配列は千鳥型に配置された場合は、供給水を受圧する時の応力が分散され、陥没の抑制に有利である。なお、図8には断面(シート平面に対して平行面)が円である円柱状の突起物を記載したが、多角形や楕円など、特に断面形状については限定しない。また、異なる断面の凸部が混在していてもよい。また、図9に示すような溝が一方向に並んで連続した溝を有する凹凸形状であってもよい。上記溝は、透過水を最短距離で集水管へと導入するために、集水管の長手方向に対して垂直方向に連続していることが好ましい。
本発明の分離膜エレメントは、例えばRO浄水器などの水処理システムに適用することができる。特に、造水能・脱塩能に優れる分離膜を搭載し、かつ回収率(供給水量に対する透過水量の割合)を高く設定して運転する場合、膜面に供給される有機ファウラント量や無機スケール量が上昇し、それに伴うファウリングの発生、浸透圧増加による分離膜エレメント有効圧の低下が起こり、分離膜エレメントの脱塩率と造水性が低下する傾向になる。しかしながら、本発明の分離膜エレメントでは、膜面線速が向上することで濃度分極が低減し、乱流効果が増すため、ファウリングの発生を抑制できるため、回収率を60%以上に設定して運転しても長期にわたり、造水能・脱塩能に優れる。
供給側流路材の1つの空隙に対して、供給側流路材を構成する繊維状物Aと、繊維状物Bの交点とそれと隣り合わない上記交点との距離をキーエンス製高精度形状測定システムKS-1100を用いて測定し、得られた2種類の距離のうち、短い方を測定した。同様の測定を30箇所の空隙に関して実施し、その距離の平均値を繊維状物の交点間隔とした。
供給側流路材の無作為に選択した部分について平面で100mm2切り出し、平面上部から観察して繊維状物Aと繊維状物Bが交わる点数を数えた。次に、同じ供給側流路材の別の平面について同様の操作を合計30回実施し、その平均値を交点密度(個/100mm2)とした。
(繊維状物Aおよび繊維状物Bの構成繊維径)
株式会社ミツトヨ製シックネスゲージ(品番547-315)を用いて繊維状物Aおよび繊維状物Bの厚みを30箇所測定し、その平均値を繊維状物Aおよび繊維状物Bの構成繊維径とした。
繊維状物Aおよび繊維状物Bからなる網目状の供給側流路材(ネット)の交点の厚みを、株式会社ミツトヨ製シックネスゲージ(品番547-315)を用いて30箇所測定し、その平均値を供給側流路材の厚みとした。
網目状の供給側流路材を構成する、無作為に選択した30本の繊維状物Aと、その隣接する繊維状物A間の距離をキーエンス製高精度形状測定システムKS-1100を用いて測定し、その平均値を繊維状物A間の距離とした。
(分離膜aの作製)
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17.0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(厚み130μm)ロールを作製した。
(分離膜bの作製)
ポリエステル不織布(通気度0.5~1cc/cm2/sec)上にポリスルホンの15.7質量%DMF溶液を200μmの厚みで、室温(25℃)でキャストし、ただちに純水中に浸漬して5分間放置することによって微多孔性支持膜(厚さ210~215μm)を作製した。
得られた微多孔性支持膜を、m-PDAの1.8質量%水溶液中に2分間浸漬し、該支持膜を垂直方向にゆっくりと引き上げ、エアーノズルから窒素を吹き付け支持膜表面から余分な水溶液を取り除いた後、TMC0.065質量%、およびウンデカン酸0.1質量%を含む25℃のn-デカン溶液を表面が完全に濡れるように塗布してから1分間静置した。次に、膜から余分な溶液を除去するために膜を1分間垂直に保持して液切りした。その後、80℃の熱水で2分間洗浄して複合分離膜ロールを得た。この分離膜を分離膜bとした。
(分離膜cの作製)
ポリエステル不織布(通気度0.5~1cc/cm2/sec)上にポリスルホンの15.7質量%DMF溶液を200μmの厚みで、室温(25℃)でキャストし、ただちに純水中に浸漬して5分間放置することによって微多孔性支持膜(厚み210~215μm)を作製した。
得られた微多孔性支持膜を、m-PDAの1.8質量%水溶液中に2分間浸漬し、該支持膜を垂直方向にゆっくりと引き上げ、エアーノズルから窒素を吹き付け支持膜表面から余分な水溶液を取り除いた後、TMC0.065質量%、およびウンデカン酸0.1質量%を含む25℃のn-デカン溶液を表面が完全に濡れるように塗布してさらに10秒後に、ジエチレングリコールジメチルエーテル1質量%n-デカン溶液を表面が完全に濡れるように塗布して1分間静置した。次に、膜から余分な溶液を除去するために膜を1分間垂直に保持して液切りした。その後、80℃の熱水で2分間洗浄して複合分離膜ロールを得た。この分離膜を分離膜cとした。
(分離膜dの作製)
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17.0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(厚み130μm)ロールを作製した。
(分離膜e、f、g、hの作製)
抄紙法で製造されたポリエステル繊維からなる不織布(通気度1.0cc/cm2/sec)上に、ポリスルホンの15質量%DMF溶液を室温(25℃)で、かつ塗布厚み180μmでキャストした後、ただちに純水中に5分間浸漬することによって基材上に多孔性支持層を形成し、多孔性支持膜を作製した。
分離膜作製時のアミンとトリメシン酸クロリドとの接触時の膜面温度を40℃、界面重合時の膜面温度を10℃と変更した分離膜を分離膜f、分離膜作製時のアミンとトリメシン酸クロリドとの接触時の膜面温度を70℃、界面重合時の膜面温度を10℃と変更した分離膜を分離膜g、分離膜作製時のアミンとトリメシン酸クロリドとの接触時の膜面温度を60℃、界面重合時の膜面温度を10℃と変更した分離膜を分離膜hとして作製した。
(分離膜のフラックス)
分離膜を47cm2に切り出し、膜評価セルにて、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0.41MPa、温度25℃、回収率1%以下の条件下で15分間運転した後に1分間のサンプリングを行い、1日当たりの透水量を、分離膜フラックス(m3/m2/日)とした。
純水透過係数は以下の方法によって計算した。
尚、溶質反射係数は以下の方法で求めることができる。まず、非平衡熱力学に基づいた逆浸透法の輸送方程式として、以下の式が知られている。
Jv=Lp(ΔP-σ・Δπ) ・・・(b)
Js=P(Cm-Cp)+(1-σ)C・Jv ・・・(c)
ここで、Jvは溶液の膜透過流束(m3/m2/s)、Lpは純水透過係数(m3/m2/s/Pa)、ΔPは膜両側の圧力差(Pa)、σは溶質反射係数、Δπは膜両側の浸透圧差(Pa)、Jsは溶質の膜透過流束(mol/m2/s)、Pは溶質透過係数(m/s)、Cmは溶質の膜面濃度(mol/m3)、Cpは透過液濃度(mol/m3)、Cは膜両側の濃度(mol/m3)、である。膜両側の平均濃度Cは、逆浸透膜のように両側の濃度差が非常に大きな場合には実質的な意味を持たない。そこで、式(a)を膜厚について積分した次式がよく用いられる。
R=σ(1-F)/(1-σF) ・・・(d)
ただし、
F=exp{-(1-σ)Jv/P} ・・・(e)
であり、Rは真の阻止率で、
R=1-Cp/Cm ・・・(f)
で定義される。ΔPを種々変化させることにより(b)式からLpを算出でき、またJvを種々変化させてRを測定し、Rと1/Jvをプロットしたものに対して(d)、(e)式をカーブフィッティングすることにより、Pとσとを同時に求めることができる。
R=100×Jv/(Jv+P)・・・(g)
(分離膜エレメントの造水量)
以下に示す3種の評価条件に基づき、分離膜エレメントの評価を実施した。
(条件1)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0.41MPa、温度25℃の条件下で15分間運転した後に1分間のサンプリングを行い、1日当たりの透水量を造水量(GPD(ガロン/日))として表した。
(条件2)供給水として、NaCl、CaCl2、Na2SO4が含まれる塩濃度200ppm、pH6.5の水溶液を用い、運転圧力0.41MPa、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日当たりの透水量を造水量(m3/日)として示した。また、分離膜エレメントの総造水量が3000Lに達したときにも1分間のサンプリングを行い、1日当たりの透水量を造水量(m3/日)として示した。
(条件3)供給水として、全炭素(TC)35ppm、全有機炭素(TOC)3.8ppm、TDS濃度350ppm、pH7.3の中国上海市水道水を用い、運転圧力0.41MPa、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日当たりの透水量を造水量(m3/日)として示した。また、分離膜エレメントの総造水量が3000Lに達したときにも1分間のサンプリングを行い、1日当たりの透水量を造水量(m3/日)として示した。また、分離膜エレメントの総造水量が3000Lに達したときにも1分間のサンプリングを行い、1日当たりの透水量を造水量(m3/日)として示した。
(回収率)
造水量の測定において、所定の時間に供給した供給水流量VFと、同時間での透過水量VPの比率を回収率とし、VP/VF×100から算出した。
(脱塩率(TDS除去率))
分離膜エレメントの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、下記式から脱塩率を算出した。
(緯編物による透過側流路材トリコットの作製)
緯編物は、ポリエチレンテレフタレートフィラメント(融点:255℃)にポリエチレンテレフタレート系低融点ポリエステルフィラメント(融点:235℃)を混繊してなるマルチフィラメント糸(48フィラメント、110デシテックス)を編糸として、天竺編の緯編組織(ゲージ(編機の単位長間にあるニードルの本数))を編成し、それを245℃で熱セット処理した後にカレンダ加工を施して透過側流路材トリコット作製した。
(不織布上に突起物を有する透過側流路材の作製)
スリット幅0.5mm、ピッチ0.9mmの櫛形シムを装填したアプリケーターを用いて、バックアップロールを20℃に温度調節しながら、分離膜エレメントとした場合に集水管の長手方向に対して垂直かつ封筒状膜とした場合に巻回方向の内側端部から外側端部まで集水管の長手方向に対して垂直になるよう直線状もしくは不連続状に、高結晶性PP(MFR1000g/10分、融点161℃)60質量%と低結晶性α-オレフィン系ポリマー(出光興産株式会社製;低立体規則性ポリプロピレン「L-MODU・S400」(商品名))40質量%からなる組成物ペレットを樹脂温度205℃、走行速度10m/分で直線状に不織布上に塗布した。不織布は厚み0.07mm、目付量が35g/m2、エンボス柄(φ1mmの円形、ピッチ5mmの格子状)であった。
(貫通孔を有するフィルムによる透過側流路材の作製)
無延伸ポリプロピレンフィルム(東レ製 トレファン(登録商標))にインプリント加工およびCO2レーザ加工を施し、貫通孔を有する透過側流路材を得た。具体的には切削加工により溝を形成した金属金型で無延伸ポリプロピレンフィルムを挟み込み、140℃/2分間/15MPaで保圧し、40℃で冷却後に金型から取り出した。
(無機スケール付着量)
(条件3)にて評価を実施した、総造水量3000Lに達した分離膜エレメントを解体し、膜面付着物を1wt%の硝酸水溶液で抽出し、日立株式会社製P-4010型ICP(高周波誘導結合プラズマ発光分析)装置を用いて、無機成分(カルシウム、マグネシウム、バリウム)の合計吸着量(g)を測定し、分離膜エレメントの膜面積から無機スケール付着量(g/m2)を算出した。
(総付着物量)
(条件3)にて評価を実施した、総造水量3000Lに達した分離膜エレメントを解体し、膜面に付着した付着物をゴム製のスクレーパーで収集した後、120℃で2時間乾燥させて質量を測定し分離膜エレメントの膜面積から総付着物量(g/m2)を算出した。
(有機ファウリング付着量)
上記総付着物量と上記無機スケール付着量の差を、有機ファウリング付着量(g/m2)として算出した。
(透過側流路材の厚みおよび凸部の高さ)
透過側流路材の厚みと凸部の高さはキーエンス社製高精度形状測定システムKS-1100で測定した。具体的には、キーエンス社製高精度形状測定システムKS-1100を用い、5cm×5cmの測定結果から平均の高低差を解析した。10μm以上の高低差のある30箇所を測定し、その平均値を凸部の高さとした。
(透過側流路材の凸部の幅および長さ、凹部の溝幅および溝長さ)
キーエンス社製高精度形状測定システムKS-1100を用い、上記の透過側流路材の厚みおよび凸部の高さと同様の手法で測定した。
(透過側流路材の凸部のピッチ)
キーエンス社製高精度形状測定システムKS-1100を用い、分離膜の透過側における流路材の頂点から、隣の流路材の頂点までの水平距離を200箇所について測定し、その平均値を凸部のピッチとした。
(透過側流路材の横断面積比)
透過側流路材を分離膜エレメントに充填した際、集水管の長手方向と平行な方向に沿って透過側流路材の凸部を通るように切断し、その断面について、顕微鏡画像解析装置を用いて凸部の中心と隣接する凸部の中心の距離(ピッチとも言う)と透過側流路材の高さを測定し、それらの積に対する、凸部の中心と隣接する凸部の中心との間に占める透過側流路材の横断面積の割合(横断面積比)を算出した。同様の測定を30箇所に関して実施し、その距離の平均値を表2中に示した。
(実施例1)
上述の製法で得られた分離膜aを断裁加工し、表2に示すポリプロピレン製ネット(厚み:300μm、交点間隔:8mm、繊維径:0.15mm、傾斜角:90°)を供給側流路材として挟んで折り畳み、リーフを作製した。
表1~3の通りに分離膜エレメント径、分離膜、供給側流路材、透過側流路材、原水供給部の位置、回収率を変更し、分離膜エレメントを作製した。
(比較例1~13)
表1~3の通りに分離膜エレメント径、分離膜、供給側流路材、透過側流路材、原水供給部の位置、回収率を変更し、分離膜エレメントを作製した。
11 繊維状物A
12 繊維状物B
101 供給水
102 透過水
103 濃縮水
2 分離膜
3 透過側流路材
4 集水管
5、5B、5C 分離膜エレメント
6 凸部
7 凹部
82 多孔性部材
821 孔
91 孔無端板
92、93、94 孔付端板
a、b 繊維状物の交点間隔
c、d 繊維状物の構成繊維径
e、f 供給側流路材の繊維状物の傾斜角
D 溝幅
E 溝長さ
H0 透過側流路材の厚み
H1 透過側流路材の凸部の高さ
S、S1、S2 透過側流路材の凸部の横断面積
P 透過側流路材の凸部の中心と隣接する凸部の中心の距離
W 透過側流路材の凸部の幅
X 透過側流路材の凸部の長さ
Claims (10)
- 集水管と、供給側の面と透過側の面とを備える分離膜と、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、
前記分離膜、供給側流路材および透過側流路材は前記集水管の周りにスパイラル状に巻囲され、
前記供給側流路材は、互いに交差する複数の繊維状物を備え、
前記供給側流路材の厚みが0.15mm以上0.50mm以下であり、
前記分離膜は、供給水を濃度200ppmの食塩水、pH6.5のNaCl水溶液とし、運転圧力0.41MPa、温度25℃の条件下でろ過した際の溶液透過係数をA(m/秒/MPa)、溶質透過係数をB(m/秒)とした際に、A3/B(m2/秒2/MPa3)の値が8.0×10-8以上である、分離膜エレメント。 - 前記分離膜は、供給水を濃度200ppmの食塩水、pH6.5のNaCl水溶液とし、運転圧力0.41MPa、温度25℃の条件下でろ過した際の透過水量が1.5m3/m2/日以上である、請求項1に記載の分離膜エレメント。
- 前記供給側流路材の交点密度が3個/100mm2以下である、請求項1又は2に記載の分離膜エレメント。
- 前記供給側流路材の交点密度が15個/100mm2以上210個/100mm2以下である、請求項1又は2に記載の分離膜エレメント。
- 前記供給側流路材により形成される供給側流路が、前記集水管の長手方向に対して垂直方向に形成されている、請求項1~4のいずれか一項に記載の分離膜エレメント。
- 前記透過側流路材は、複数の突起物が形成されたシート又は複数の突起物が固着されたシートである、請求項1~5のいずれか一項に記載の分離膜エレメント。
- 前記突起物が、前記集水管の長手方向に対して垂直方向に連続している、請求項6に記載の分離膜エレメント。
- 前記透過側流路材の横断面が複数の透過側流路を形成し、かつ、前記透過側流路材の横断面積比が0.4以上0.75以下である、請求項1~7のいずれか一項に記載の分離膜エレメント。
- 請求項1~8のいずれか一項に記載の分離膜エレメントを用いて、供給された水量の60%以上を造水する、分離膜エレメントの運転方法。
- 請求項1~8のいずれか一項に記載の分離膜エレメントを用いて、供給された水量の40%以下を造水する、分離膜エレメントの運転方法。
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JP (1) | JP6973081B2 (ja) |
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WO2019235441A1 (ja) * | 2018-06-04 | 2019-12-12 | 国立大学法人信州大学 | 半透複合膜及びその製造方法並びに半透複合膜エレメント |
KR20210039953A (ko) * | 2019-10-02 | 2021-04-12 | 주식회사 엘지화학 | 공급측 유로재 및 분리막 엘리먼트 |
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US20190282962A1 (en) | 2019-09-19 |
US11511233B2 (en) | 2022-11-29 |
JP6973081B2 (ja) | 2021-11-24 |
KR20190049744A (ko) | 2019-05-09 |
KR102326947B1 (ko) | 2021-11-15 |
CN109715275A (zh) | 2019-05-03 |
CN109715275B (zh) | 2021-12-31 |
JPWO2018056090A1 (ja) | 2019-07-04 |
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