WO2015060286A1 - 正浸透用中空糸膜エレメント及び膜モジュール - Google Patents
正浸透用中空糸膜エレメント及び膜モジュール Download PDFInfo
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- WO2015060286A1 WO2015060286A1 PCT/JP2014/077910 JP2014077910W WO2015060286A1 WO 2015060286 A1 WO2015060286 A1 WO 2015060286A1 JP 2014077910 W JP2014077910 W JP 2014077910W WO 2015060286 A1 WO2015060286 A1 WO 2015060286A1
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- fiber membrane
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- 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
- B01D63/02—Hollow fibre modules
- B01D63/025—Bobbin units
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- 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
- B01D61/002—Forward osmosis or direct osmosis
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- the present invention relates to a forward osmosis hollow fiber membrane element and a membrane module that are excellent in contamination resistance, have a small flow pressure loss in the hollow portion of the hollow fiber membrane, and have a large amount of membrane permeated water. More specifically, the present invention relates to fresh water with a driving force that is a concentration reduction of organic matter, volume reduction by recovery or drainage concentration, seawater desalination, or a concentration difference between a low concentration aqueous solution and a high concentration pressurized aqueous solution.
- the energy can be generated by rotating the turbine with the flow rate and pressure of the high-concentration aqueous solution in the pressurized state increased by the permeated fresh water.
- it can be used for fresh water treatment for generating energy such as electric power by utilizing osmotic pressure due to a concentration difference between seawater or concentrated seawater and fresh water.
- Separation and concentration of liquid mixtures by membrane separation is an energy-saving method because it does not involve phase changes compared to conventional separation techniques such as distillation, and it does not involve changes in the state of substances. It is widely used in many fields such as food separation such as separation of organic matter and recovery of organic matter from industrial wastewater. Membrane water treatment has become established as an indispensable process that supports state-of-the-art technology.
- Such a water treatment using a membrane is used as a membrane module in which membranes are assembled into a pressure vessel by assembling membranes into one constituent element.
- a hollow fiber membrane element is a spiral membrane element.
- the water permeability per unit membrane area is not large, but since the membrane area per membrane module volume can be increased, the overall water permeability can be increased and the volume efficiency is very high. Excellent compactness. Further, when both the high-concentration aqueous solution and the fresh water are supplied into the module and brought into contact via the semipermeable membrane, the concentration polarization on the membrane surface can be kept small.
- a double-ended opening type is used from the viewpoint of efficiency (see Patent Documents 1 and 2).
- the flow of membrane permeated water flows from the outside to the inside (inside the hollow portion) of the hollow fiber membrane and flows out from the openings at both ends, as shown in the explanatory diagram of FIG.
- the flow length of the membrane permeate flowing through the hollow portion is about half of the total length of the hollow fiber membrane.
- the seawater flows outside the hollow fiber membrane and the outside of the hollow fiber membrane is pressurized, a flow occurs in a direction in which the contaminants are pressure-bonded to the membrane surface, and dirt components in the seawater are adjacent to each other. There is a tendency to trap and deposit between hollow fiber membranes, contaminating membrane elements and adversely affecting performance.
- the fresh water that is the source of the membrane permeated water flows through the hollow portion of the hollow fiber membrane, and flows from one end of the hollow fiber membrane to the other end,
- the flow length is the total length of the hollow fiber membrane. Therefore, the flow pressure loss in the hollow portion in the case of the forward osmosis membrane (FO membrane) is extremely larger than that in the case of the reverse osmosis membrane (RO membrane).
- the contamination resistance is improved by cross-disposing the hollow fiber membranes constituting the membrane element. Specifically, by forming the intersection of the hollow fiber membranes, the gap between the hollow fiber membranes is secured, the occurrence of drift and concentration polarization is suppressed, and the turbidity component of seawater is added to the outer surface of the hollow fiber membrane. It is hard to collect. In this case, it is preferable that the number of winds per element length of the hollow fiber membranes arranged in a crossing direction is large, and as a result, the number of crossing portions of the hollow fiber membranes increases, and the contamination resistance is improved.
- the RO membrane of Patent Document 1 discloses a wind number of 2. Also, the RO membrane of Patent Document 2 is specifically disclosed having a wind number of 2.
- the present invention was devised in view of the current state of the prior art described above, and the object thereof is a forward osmosis hollow fiber membrane element having excellent contamination resistance and low flow pressure loss (having a sufficient amount of permeated water), And providing a membrane module using the same.
- the present inventor in particular, when performing the cross-arrangement with the hollow fiber membrane for forward osmosis, particularly the length of the hollow fiber membrane Even if the number of winds in the outer layer of the hollow fiber membrane roll is long, the flow direction of the membrane permeate is in the opposite direction to that of the reverse osmosis membrane.
- the present invention has been completed by finding that it is extremely small, and by doing so, the influence of a decrease in the amount of permeated water due to high flow pressure loss can be neglected.
- the present invention has the following configurations (1) to (5).
- a hollow fiber membrane element of both ends opening type in which both ends of a hollow fiber membrane winding body in which the hollow fiber membranes are arranged in a cross shape by opening the hollow fiber membrane spirally around the porous pipe are opened. Because a) In the range from the outermost layer of the hollow fiber membrane wound body to at least 1/8 of the thickness of the wound body, the number of winds per element length is 0.33 to 1.75, b) A hollow fiber membrane for forward osmosis, wherein the number of winds per element length is more than 1.75 in the range from the innermost layer of the hollow fiber membrane roll to at least 1/4 of the thickness of the roll. element.
- the number of winds per element length is 0.33 to 1.75 in the range from the outermost layer of the hollow fiber membrane wound body to the maximum 3/4 of the thickness of the wound body (1 ) Hollow fiber membrane element for forward osmosis.
- the hollow fiber membrane is composed of one or more kinds of resins selected from the group consisting of cellulose acetate-based resins, polyamide-based resins, and sulfonated polysulfone-based resins.
- the hollow fiber membrane element and the hollow fiber membrane module of the present invention have a number of winds per element length, compared to the conventional reverse osmosis type, in particular, the hollow fiber membrane has a considerably smaller outer layer part, so that the normal osmosis The influence of the flow pressure loss of the fluid in the hollow portion during operation can be reduced, and as a result, a high amount of membrane permeate can be obtained. Further, even if the number of winds is reduced within the range defined by the present invention, high contamination resistance is maintained during forward osmosis operation, unlike reverse osmosis.
- the forward osmosis in which the membrane element of the present invention is used is obtained by bringing an aqueous solution having a high concentration and a high osmotic pressure into contact with an aqueous solution having a low concentration and a low osmotic pressure through a semipermeable membrane.
- This is a water treatment method that utilizes the phenomenon that fresh water moves to the higher aqueous solution side.
- the hollow fiber membrane element of the present invention can take a larger membrane area per element than a spiral flat membrane, and depending on the size of the hollow fiber membrane, About 10 times as large as the membrane area can be obtained. Therefore, the hollow fiber membrane may have a very small amount of treatment per unit membrane area when obtaining the same water permeation amount, and can reduce the contamination of the membrane surface that occurs when the supply water permeates the membrane as compared to the spiral type. The operation time until the membrane is washed can be increased. Furthermore, since the drift in the element is unlikely to occur, it is preferable when water treatment is performed using the concentration difference as a driving force.
- the material of the hollow fiber membrane of the present invention is not particularly limited as long as a high separation performance equivalent to a reverse osmosis membrane can be expressed.
- sulfonated polysulfone resins such as cellulose acetate resin, sulfonated polysulfone, and sulfonated polyethersulfone are resistant to chlorine as a fungicide, and can easily suppress the growth of microorganisms. preferable.
- cellulose acetates cellulose triacetate is preferable from the viewpoint of durability.
- the outer diameter of the hollow fiber membrane of the present invention is preferably 160 to 270 ⁇ m. If the outer diameter is smaller than the above range, the inner diameter inevitably becomes smaller, so the same problem as the above-mentioned inner diameter may occur. On the other hand, if the outer diameter is larger than the above range, the membrane area per unit volume in the module cannot be increased, and the compactness that is one of the merits of the hollow fiber membrane module is impaired.
- the hollow ratio of the hollow fiber membrane of the present invention is preferably 20 to 42%.
- the inner diameter of the hollow fiber membrane of the present invention may be in a range satisfying the hollow ratio with respect to the preferable outer diameter, and is preferably 70 to 175 ⁇ m.
- the inner diameter is smaller than the above range, the pressure loss of the fluid flowing through the hollow portion is generally increased, and therefore an excessively high pressure is required to flow a desired fresh water flow rate when the length of the hollow fiber membrane is relatively long. This can cause energy loss.
- the inner diameter is larger than the above range, there is a trade-off relationship between the hollow ratio and the module membrane area, and it may be necessary to sacrifice either the durability at the working pressure or the membrane area per unit volume.
- the hollow fiber membrane element of the present invention is obtained by sealing both ends of a hollow fiber membrane winding body with a resin, then cutting a part of the resin and opening both ends of the hollow fiber membrane.
- the body is formed by laminating the hollow fiber membranes in the radial direction by winding a hollow fiber membrane or a bundle of hollow fiber membranes spirally around the porous pipe. In that case, the hollow fiber membranes are arranged in a cross shape.
- FIG. 3 shows a schematic diagram of an example of the hollow fiber membrane element of the present invention in which the hollow fiber membranes are arranged in a cross shape. By adopting the intersection arrangement, voids are regularly formed at the intersection of the hollow fiber membranes.
- the porous distribution pipe is a tubular member having a function of distributing the fluid supplied from the supply fluid inlet to the hollow fiber membrane aggregate when supplying the supply liquid to the outside of the hollow fiber membrane.
- the porous pipe is preferably located at the center of the hollow fiber membrane assembly. If the diameter of the porous pipe is too large, the area occupied by the hollow fiber membrane in the membrane module is reduced, and as a result, the membrane area of the membrane element or membrane module is reduced, so that the water permeability per volume may be reduced. Further, if the diameter of the porous pipe is too small, the pressure loss increases when the supply fluid flows through the porous pipe, and as a result, the effective differential pressure applied to the hollow fiber membrane may be reduced and the processing efficiency may be reduced. .
- the strength may be reduced, and the porous pipe may be damaged by the tension of the hollow fiber membrane that is received when the supply fluid flows through the hollow fiber membrane layer. It is important to set an optimum diameter in consideration of these influences comprehensively.
- the area ratio of the cross-sectional area of the porous pipe to the cross-sectional area of the hollow fiber membrane element is preferably 4 to 20%.
- the outer diameter of the hollow fiber membrane wound body is preferably 130 to 420 mm. If the outer diameter is too large, operability in maintenance management such as membrane exchange work may be deteriorated. If the outer diameter is too small, the membrane area per unit membrane element is reduced, the processing amount is reduced, and this is not preferable from the viewpoint of economy.
- the length of the hollow fiber membrane wound body is preferably 0.2 to 1.6 m. When this length is too long, the flow pressure loss inside the hollow of the hollow fiber membrane increases, and the forward osmosis performance can be lowered. If it is too short, the membrane area per unit membrane element is reduced and the amount of treatment is reduced, which is not preferable from the viewpoint of economy.
- the filling rate of the hollow fiber membrane in the rolled-up hollow fiber membrane is preferably 40 to 65%. If the filling rate is too large, the gap between the hollow fiber membranes becomes too small, and the effect of the cross arrangement is hardly exhibited. On the other hand, when the filling rate is too small, the number of hollow fiber membranes is small and the membrane area is small.
- the number of winds per element length of the hollow fiber membranes arranged in an intersecting manner ranges from the outermost layer of the hollow fiber membrane wound body to at least 1/8 of the thickness of the wound body (outer layer Part)), the maximum feature is that the number of winds per element length is 0.33 to 1.75.
- the wind number is more preferably 0.5 to 1.5.
- the number of winds refers to the number of windings while moving from one end to the other end of the hollow fiber membrane winding body in the case of forming the above-described crossing arrangement.
- the larger the number of winds the greater the number of intersections of the hollow fiber membranes. For example, when the number of winds is 1.0, the axial position of the intersecting portion is the central portion of the wound body.
- the angle formed by the hollow fiber membrane and the central axis of the wound body is smaller in the inner layer of the wound body of the hollow fiber membrane and larger in the outer layer portion. The angle is determined by the length and outer diameter of the wound body.
- the range of the outer layer portion of the wound body that reduces the number of winds is more effective as the hollow fiber membrane length is longer outside, but is the portion from the outermost layer to at least 1/8 of the thickness of the wound body.
- the number of winds may be reduced for a portion of about 1/8 of the thickness of the wound body from the outermost layer.
- the number of winds is reduced in a portion that is 1/4 or 1/3 of the thickness of the wound body from the outermost layer or a maximum of 3/4. It is preferable to do this.
- the portion from the outermost layer to 1/4 of the thickness of the wound body has a wind number of 0.33 to 0.75, and the portion from the outermost layer to 1/4 of the thickness of the wound body to 1/2
- the wind number is set to 0.75 to 1.25, and the wind number is set to 1.25 to 1.75 in the portion from the outermost layer to 1/2 of the thickness of the wound body to 3/4. It is also within the scope of the present invention to reduce the number of winds stepwise as it goes outside the wound body.
- the element diameter is small, there is no big problem even if the present invention is applied, but it is preferable when the element diameter is 130 mm or more because the effects of the present invention are remarkably exhibited.
- the number of winds in the inner layer is preferably more than 1.75.
- Hollow fiber membrane elements in which hollow fiber membranes are arranged in an intersecting manner have been conventionally proposed for reverse osmosis, but in all cases, the number of winds is larger than the range defined in the present invention, specifically, the number of winds is 2. is there.
- the hollow fiber membrane element for forward osmosis of the present invention when the cross arrangement of the conventional hollow fiber membrane having a wind number of 2 is adopted as it is, high contamination resistance can be obtained, but the flow pressure loss of the fluid flowing through the hollow portion Is too large to secure a sufficient amount of permeate. As apparent from the comparison between FIG. 1 and FIG.
- the hollow fiber membrane of the present invention for example, as described in Japanese Patent No. 3591618, is obtained by dividing a membrane-forming solution comprising cellulose triacetate, ethylene glycol (EG), and N-methyl-2-pyrrolidone (NMP) into three parts.
- a cellulose acetate-based hollow fiber membrane is ejected from a nozzle, immersed in a coagulating liquid consisting of water / EG / NMP through an aerial traveling section to obtain a hollow fiber membrane, and then the hollow fiber membrane is washed with water and then heat treated. Can be manufactured.
- the copolymer polyamide obtained by low-temperature solution polymerization method from terephthalic acid dichloride, 4,4'-diaminodiphenylsulfone, and piperazine, it is dissolved in a dimethylacetamide solution containing CaCl 2 and diglycerin to form a film-forming solution.
- the polyamide-based hollow fiber membrane can be produced by discharging this solution from the three-divided nozzle through the aerial running section into the coagulating liquid, washing the resulting hollow fiber membrane with water, and then heat-treating it.
- the hollow fiber membrane of the present invention obtained as described above is incorporated into a hollow fiber membrane element by a conventionally known method.
- Incorporation of hollow fiber membranes for example, as described in Japanese Patent No. 441486, Japanese Patent No. 4277147, Japanese Patent No. 3591618, Japanese Patent No. 3008886, etc.
- a plurality of hollow fiber membrane assemblies are arranged side by side as a flat hollow fiber membrane bundle and wound around a porous pipe having a large number of holes while traversing. By adjusting the length and rotation speed of the porous pipe at this time, and the traverse speed of the hollow fiber membrane bundle, the pipe is wound up so that an intersection is formed on the circumferential surface at a specific position of the wound body. Next, after bonding both ends of the wound body, both sides are cut to form a hollow fiber membrane opening to produce a hollow fiber membrane element.
- the hollow fiber membrane element for forward osmosis of the present invention produced as described above is loaded into a container, particularly a pressure vessel having pressure resistance that can withstand the operating pressure, so that the hollow fiber membrane module for forward osmosis. It can be.
- This forward osmosis hollow fiber membrane module has four nozzles as shown in FIG. Two of them are an inlet nozzle and an outlet nozzle for a high concentration solution having a high osmotic pressure, and the high concentration solution communicates with a space in contact with the outside of the hollow fiber membrane.
- the outlet nozzle communicates with a space in contact with the outermost layer portion of the hollow fiber membrane element.
- the other two places are an inlet nozzle and an outlet nozzle for low-concentration and low-concentration fresh water, and communicate with the space in contact with the open end of the hollow portion of the hollow fiber membrane.
- FIG. 7 is a graph showing the relationship between the amount of permeated water per membrane element volume and the contamination resistance (differential pressure increase rate) based on the results of Examples described later.
- the rate increases exponentially. For example, if the wind number is 2 to 1.5, the permeate amount per membrane element volume is about 1.2 times, and if the wind number is 0.5, the permeate amount is about 1.7 times.
- the rate of increase in the differential pressure tends to increase rapidly when the number of winds is less than one.
- the number of winds of the membrane element that can suppress the rate of increase in the differential pressure as much as possible while securing a larger amount of permeated water is 0.33 to 1.75, preferably 0.5 to 1. .5.
- the numerical value itself of the permeated water amount per membrane element and the differential pressure increase rate depends on the performance of the hollow fiber membrane, the numerical value itself is not particularly significant.
- FIG. 8 shows the effect of changes in the membrane element diameter.
- the membrane element diameter is preferably 130 mm or more.
- the larger the membrane element diameter the better the effect of the present invention, which is preferable.
- the upper limit is considered to be about 420 mm from the viewpoint of ease of manufacturing the membrane element.
- FIG. 9 shows the effect of the membrane element length.
- the membrane element length that exhibits performance exceeding that of the conventional RO module is preferably about 0.2 to 1.6 m.
- FIG. 10 shows the influence of the outer diameter of the hollow fiber membrane.
- the outer diameter of the hollow fiber membrane increases, the amount of permeated water increases.
- the specific outer diameter of the hollow fiber membrane is exceeded, the amount of permeated water gradually decreases. This is due to the fact that when the volume of the membrane element is kept constant, the membrane area decreases conversely as the hollow fiber membrane outer diameter is increased. From FIG. 10, it can be seen that when the hollow fiber membrane outer diameter at which the effect of the present invention is exhibited is read, performance exceeding the conventional RO module (Comparative Example 1) is exhibited in the range of about 160 ⁇ m to 270 ⁇ m.
- the hollow fiber membrane module for forward osmosis produced in this way can obtain the amount of permeated water as an osmotic flow from the difference in osmotic pressure caused by the difference in the salinity concentration of water flowing between the outside and inside (hollow part) of the hollow fiber membrane. .
- the low-concentration supply liquid can be concentrated or energy can be recovered from the osmotic flow.
- a high pressure osmotic aqueous solution (seawater) and a low pressure, low osmotic pressure fresh water are brought into contact with each other through a forward osmosis membrane, so that the low pressure fresh water has a high pressure and high osmosis through the membrane.
- the energy can be recovered by flowing into the pressurized aqueous solution and rotating the turbine or the like with the pressurized aqueous solution.
- the inner diameter and outer diameter of the hollow fiber membrane are passed through an appropriate number so that the hollow fiber membrane does not fall out into a hole of ⁇ 3 mm formed in the center of the slide glass. Cut the hollow fiber membrane with a razor along the upper and lower surfaces of the slide glass to obtain a sample of the hollow fiber membrane cross section, and then measure the short diameter and long diameter of the cross section of the hollow fiber membrane using a projector Nikon PROFILE PROJECTOR V-12. Can be obtained. The short diameter and the long diameter in two directions were measured for each cross section of the hollow fiber membrane, and the respective arithmetic average values were defined as the inner diameter and the outer diameter of the single cross section of the hollow fiber membrane. The same measurement was performed for the five cross sections, and the average values were taken as the inner and outer diameters. The hollow ratio was calculated by (inner diameter / outer diameter) 2 ⁇ 100.
- membrane area was determined from the outer diameter of the hollow fiber membrane, the number of hollow fiber membranes present in the hollow fiber membrane element, and the average effective length of the hollow fiber membranes.
- Membrane area (m 2 ) ⁇ ⁇ Outer diameter of hollow fiber membrane (m) ⁇ Number of hollow fiber membranes ⁇ Average effective length of hollow fiber membrane (m)
- the average effective length of the hollow fiber membrane was calculated as follows. The distance between the insides of the resin at the end of the element, that is, the effective length (LE) of the apparent hollow fiber membrane, the outer diameter (DO) of the element body, and the outer diameter (DI) of the porous pipe are measured.
- the average effective length can be calculated by substituting the measured value together with the wind number (WD) into the following equation.
- LO2 (LE) 2 + ( ⁇ ⁇ DO ⁇ WD) 2
- LI2 (LE) 2 + ( ⁇ ⁇ DI ⁇ WD) 2
- Average effective length ((LO2) 0.5 + (LI2) 0.5 ) / 2
- the wind number was determined from the number of windings (number of rotations) around the central axis from one end of the hollow fiber membrane of the wound body to the other end.
- the pressure is discharged from a nozzle arranged on the side of the communicating pressure vessel, and the pressure and flow rate are adjusted with a flow rate adjusting valve.
- the supply pressure of the high concentration aqueous solution is PDS1 (MPa)
- the supply flow rate is QDS1 (L / min)
- the amount of discharged water of the high concentration aqueous solution is QDS2 (L / min)
- the supply flow rate of fresh water is QFS1 (L / min)
- the outflow flow rate was QFS2 (L / min) and the freshwater outflow pressure was PFS2 (kPa)
- the flow rate increment (QDS2-QDS1) of the high-concentration aqueous solution under the conditions was measured as the amount of permeated water of the module.
- a high concentration aqueous solution is obtained by performing continuous operation under the same operating conditions as the above-mentioned measurement of water permeability, except that highly contaminated simulated seawater for measuring contamination resistance is used instead of the high concentration aqueous solution.
- the rate of contamination of the hollow fiber membrane element was measured as a rate.
- composition of this highly polluted simulated seawater is that reverse osmosis membrane treated water has a sodium chloride concentration of 70 g / L, sodium alginate 0.8 g / L, colloidal silica (PL-7) 90 mg-SiO 2 / L, ferric chloride. Consists of 10 mg / L of hexahydrate.
- Example 1 Cellulose triacetate (CTA, Daicel Chemical Industries, LT35) 41% by weight, N-methyl-2-pyrrolidone (NMP, Mitsubishi Chemical) 50% by weight, ethylene glycol (EG, Mitsubishi Chemical) 8.7% by weight, Benzoic acid (Nacalai Tesque) 0.3% by weight was uniformly dissolved at 180 ° C. to obtain a film forming stock solution.
- the obtained film-forming stock solution was degassed under reduced pressure, and then discharged from an arc-type (three-division) nozzle into a space cut off from the outside air at 163 ° C. After passing through a space time of 0.03 seconds, NMP / EG / It was immersed in a 12 ° C.
- the hollow fiber membrane was washed by a multistage inclined submerged washing method and shaken off in a wet state.
- the obtained hollow fiber membrane was immersed in water at 90 ° C. and subjected to hot water treatment for 20 minutes.
- the obtained hollow fiber membrane had an inner diameter of 85 ⁇ m and an outer diameter of 175 ⁇ m.
- the obtained hollow fiber membranes were arranged in an intersecting manner around the porous pipes to form an aggregate of hollow fiber membranes.
- the bundle of hollow fiber membranes was traversed while rotating the porous pipe around its axis, and the hollow fiber membranes were arranged in an intersecting manner by winding around the porous pipe.
- both ends of the hollow fiber membrane assembly were fixed by potting with an epoxy resin, the both ends of the resin portion were cut to open the hollow portion of the hollow fiber membrane, thereby producing a hollow fiber membrane element.
- the number of winds per element length is 0.5 in the portion (outer layer portion) from the outermost layer of the hollow fiber membrane wound body to 3/4 of the thickness of the wound body.
- the number of winds per element length of the portion (inner layer portion) was 2.0, the length was about 70 cm, the outer diameter was 130 mm, the filling rate of the hollow fiber membrane was 51%, and the membrane area was 67 m 2 .
- the hollow fiber membrane element was loaded into a pressure vessel and various tests were conducted as a module. The results are shown in Table 1 together with details of the hollow fiber membrane and elements.
- Example 2 Using the same hollow fiber membrane as in Example 1, a hollow fiber membrane element was prepared in the same manner as in Example 1 except that the number of winds in the outer layer portion was changed to 1.0. The hollow fiber membrane element was loaded into a pressure vessel and various tests were conducted as a module. The results are shown in Table 1 together with details of the hollow fiber membrane and elements.
- Example 3 A hollow fiber membrane element was produced in the same manner as in Example 1 except that the number of winds in the outer layer portion was changed to 1.5 using the same hollow fiber membrane as in Example 1.
- the hollow fiber membrane element was loaded into a pressure vessel and various tests were conducted as a module. The results are shown in Table 1 together with details of the hollow fiber membrane and elements.
- Example 4 Using the same hollow fiber membrane as in Example 1, in the outer layer portion (the portion from the outermost layer of the hollow fiber membrane roll-up body to 1/8 of the thickness of the roll-up body), the number of winds per element length is 1.0, A hollow fiber membrane element was prepared in the same manner as in Example 1 except that the number of winds in the other part (inner layer part) was changed to 2.0. The hollow fiber membrane element was loaded into a pressure vessel and various tests were conducted as a module. The results are shown in Table 1 together with details of the hollow fiber membrane and elements.
- Example 5 Using the same hollow fiber membrane as in Example 1, the outer diameter of the element is 420 mm, and the outer layer portion (the portion from the outermost layer of the hollow fiber membrane roll-up body to 3/4 of the thickness of the roll-up body) per element length A hollow fiber membrane element was produced in the same manner as in Example 1 except that the number of winds was changed to 1.0 and the number of winds in other parts (inner layer part) was changed to 2.0. The hollow fiber membrane element was loaded into a pressure vessel and various tests were conducted as a module. The results are shown in Table 1 together with details of the hollow fiber membrane and elements.
- Example 1 Comparative Example 1 Using the same hollow fiber membrane as in Example 1, a hollow fiber membrane element was prepared in the same manner as in Example 1 except that the number of winds in both the inner layer part and the outer layer part was changed to 2.0. The hollow fiber membrane element was loaded into a pressure vessel and various tests were conducted as a module. The results are shown in Table 1 together with details of the hollow fiber membrane and elements.
- Example 2 A hollow fiber membrane element was prepared in the same manner as in Example 1 except that the same hollow fiber membrane as in Example 1 was used and the number of winds in the outer layer portion was changed to 0.25.
- the hollow fiber membrane element was loaded into a pressure vessel and various tests were conducted as a module. The results are shown in Table 1 together with details of the hollow fiber membrane and elements.
- Example 3 Using the same hollow fiber membrane as in Example 1, the outer layer (the portion from the outermost layer of the hollow fiber membrane roll-up body to 1/10 of the thickness of the roll-up body) has a wind number of 1.0, and the other parts ( A hollow fiber membrane element was produced in the same manner as in Example 1 except that the number of winds in the inner layer portion was changed to 2.0. The hollow fiber membrane element was loaded into a pressure vessel and various tests were conducted as a module. The results are shown in Table 1 together with details of the hollow fiber membrane and elements.
- Example 6 After purifying the copolymerized polyamide obtained by low temperature solution polymerization method from terephthalic acid dichloride, 70 mol% 4,4'-diaminodiphenylsulfone and 30 mol% piperazine, 36 parts by weight of this was added 4 parts by weight of CaCl 2 (into the polymer). And a dimethylacetamide solution containing 3.6 parts by weight of diglycerin (relative to the polymer) at 80 ° C. to obtain a film-forming solution. After defoaming this solution, the solution was discharged from a three-part nozzle and immersed in a coagulating liquid cooled to 4 to 6 ° C. through an aerial traveling part to obtain a hollow fiber membrane. Next, the resulting hollow fiber membrane was washed with water and then heat-treated at 75 to 85 ° C. for 30 minutes. The obtained hollow fiber membrane had an inner diameter of 100 ⁇ m and an outer diameter of 200 ⁇ m.
- the obtained hollow fiber membranes were arranged in an intersecting manner around the porous pipes to form an aggregate of hollow fiber membranes.
- the bundle of hollow fiber membranes was traversed while rotating the porous pipe around its axis, and the hollow fiber membranes were arranged in an intersecting manner by winding around the porous pipe. After both ends of the hollow fiber membrane aggregate were potted and fixed with an epoxy resin, both ends of the resin portion were cut to open the hollow portions of the hollow fiber membranes to produce hollow fiber membrane elements.
- the number of winds of the outer layer portion of the obtained hollow fiber membrane element (the portion from the outermost layer of the hollow fiber membrane roll to 3/4 of the thickness of the roll) is 1.0, and the wind of the other portion (inner layer) The number was 2.0, the length was about 70 cm, the outer diameter was 130 mm, the filling rate of the hollow fiber membrane was 51%, and the membrane area was 58 m 2 .
- the hollow fiber membrane element was loaded into a pressure vessel and various tests were conducted as a module. The results are shown in Table 1 together with details of the hollow fiber membrane and elements.
- Example 7 3,3′-Disulfo-4,4′-dichlorodiphenylsulfone disodium salt (S-DCDPS) 11.5 mol%, 2,6-dichlorobenzonitrile (DCBN) 38.5 mol%, 4,4′-biphenol 50 mol % Of the sulfonated polyarylethersulfone (SPN-23) obtained by polymerizing 1% by weight was previously dried at 110 ° C. for 12 hours, and then weighed 80 parts by weight. Thus, a film forming solution was obtained. This film-forming solution was maintained at 150 ° C., and EG was discharged as an internal liquid from a tube-in-orifice nozzle.
- S-DCDPS 3,3′-Disulfo-4,4′-dichlorodiphenylsulfone disodium salt
- DCBN 2,6-dichlorobenzonitrile
- SPN-273 sulfonated polyarylethersulfone
- the air gap length was 20 mm, and it was immersed in a coagulation bath composed of 3.5% by weight salt water. Subsequently, the hollow fiber membrane was washed by a multistage inclined submerged washing method and shaken off in a wet state. The obtained hollow fiber membrane was immersed in salt water having a concentration of 14.5% by weight, and annealed at a temperature of 98 ° C. for 20 minutes.
- the obtained hollow fiber membranes were arranged in an intersecting manner around the porous pipes to form an aggregate of hollow fiber membranes.
- the bundle of hollow fiber membranes was traversed while rotating the porous pipe around its axis, and the hollow fiber membranes were arranged in an intersecting manner by winding around the porous pipe. After both ends of the hollow fiber membrane aggregate were potted and fixed with an epoxy resin, both ends of the resin portion were cut to open the hollow portions of the hollow fiber membranes to produce hollow fiber membrane elements.
- the number of winds of the outer layer portion of the obtained hollow fiber membrane element (the portion from the outermost layer of the hollow fiber membrane roll to 3/4 of the thickness of the roll) is 1.0, and the wind of the other portion (inner layer) The number was 2.0, the length was about 70 cm, the outer diameter was 130 mm, the filling rate of the hollow fiber membrane was 51%, and the membrane area was 71 m 2 .
- the hollow fiber membrane element was loaded into a pressure vessel and various tests were conducted as a module. The results are shown in Table 1 together with details of the hollow fiber membrane and elements.
- the hollow fiber membrane element for forward osmosis of the present invention is designed to have a structure with high water permeability of the membrane and excellent anti-contamination property, it generates energy using forward osmosis water treatment and concentration difference as driving force. Very useful in the field.
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Abstract
Description
している。この場合、交差配置された中空糸膜のエレメント長あたりのワインド数が大きい方が好ましく、それにより中空糸膜の交差部も多くなり、耐汚染性が向上する。特許文献1のRO膜では、図面から明らかなように、ワインド数2のものが開示されている。また、特許文献2のRO膜でも、ワインド数が2のものが具体的に開示されている。
(1)多孔分配管の周りに中空糸膜を螺旋状に巻回することにより中空糸膜を交差状に配置した中空糸膜巻上げ体の両端部を開口させた両端開口型の中空糸膜エレメントであって、
a)前記中空糸膜巻上げ体の最外層から巻き上げ体の厚みの少なくとも1/8までの範囲において、エレメント長あたりのワインド数を0.33~1.75とし、
b)前記中空糸膜巻き上げ体の最内層から巻き上げ体の厚みの少なくとも1/4までの範囲において、エレメント長あたりのワインド数を1.75超としたことを特徴とする正浸透用中空糸膜エレメント。
(2)前記中空糸膜巻上げ体の最外層から巻き上げ体の厚みの最大3/4までの範囲において、エレメント長あたりのワインド数を0.33~1.75としたことを特徴とする(1)に記載の正浸透用中空糸膜エレメント。
(3)前記エレメントの外径が130mm以上であることを特徴とする(1)または(2)に記載の正浸透用中空糸膜エレメント。
(4)中空糸膜が、酢酸セルロース系樹脂、ポリアミド系樹脂、及びスルホン化ポリスルホン系樹脂からなる群から選ばれる1種以上の樹脂からなることを特徴とする(1)~(3)のいずれかに記載の正浸透用中空糸膜エレメント。
(5)中空糸膜の外径が160~270μmであることを特徴とする(1)~(4)のいずれかに記載の正浸透用中空糸膜エレメント。
(6)中空糸膜巻上げ体の外径が130~420mm、長さが0.2~1.6mであることを特徴とする(1)~(5)のいずれかに記載の正浸透用中空糸膜エレメント。
(7)(1)~(6)のいずれかに記載の正浸透用中空糸膜エレメント1本以上を容器に装填したことを特徴とする正浸透用中空糸膜モジュール。
なお、中空率(%)は下記式により求めることができる。
中空率(%)=(内径/外径)2×100
充填率(%)=中空糸膜の外径(m)2×π/4×中空糸膜本数/巻上げ体の断面積(m2)×100
一方、低ワインド数領域を中空糸膜長が短い内層部まで広げると、圧損の低減効果が小さく、耐汚染性が低下する可能性がある。したがって、内層部のワインド数は1.75超とすることが好ましい。
中空糸膜の内径、外径は、中空糸膜をスライドグラスの中央に開けられたφ3mmの穴に中空糸膜が抜け落ちない程度に適当本数通し、スライドグラスの上下面に沿ってカミソリにより中空糸膜をカットし、中空糸膜断面サンプルを得た後、投影機Nikon PROFILE PROJECTOR V-12を用いて中空糸膜断面の短径、長径を測定することにより得られる。中空糸膜断面1個につき2方向の短径、長径を測定し、それぞれの算術平均値を中空糸膜断面1個の内径および外径とした。5つの断面について同様に測定を行い、平均値を内径、外径とした。
中空率は(内径/外径)2×100で算出した。
中空糸膜巻上げ体の両端部を樹脂で封止した後、樹脂の一部を切断し中空糸膜の両端部を開口させた中空糸膜エレメントの一方の開口端部から他方の開口端部までの中心軸と平行な直線距離を測定して求めた。
中空糸膜エレメントの樹脂で封止して形成された開口端部の直径を測定した。
膜面積は、中空糸膜の外径、中空糸膜エレメントに存在する中空糸膜の本数、中空糸膜の平均有効長から求めた。
膜面積(m2)=π×中空糸膜外径(m)×中空糸膜本数×中空糸膜の平均有効長(m)
なお、中空糸膜の平均有効長は、以下のように算出した。
エレメントの端部の樹脂の内側同士の距離、すなわち見かけの中空糸膜の有効長(LE)、エレメント胴部の外径(DO)、多孔分配管の外径(DI)を測定し、これらの測定値をワインド数(WD)とともに下記の式に代入することにより、平均有効長を算出することができる。
LO2=(LE)2+(π×DO×WD)2
LI2=(LE)2+(π×DI×WD)2
平均有効長=((LO2)0.5+(LI2)0.5)/2
前述の膜エレメント径と膜エレメント長より下記式により求めた。
エレメント容積(m3)=π×エレメント端部外径(m)2/4×エレメント長(m)
ワインド数は、巻き上げ体の中空糸膜の一方の端部から他方の端部に渡るまでの中心軸に対する巻き付いている回数(回転回数)から求めた。
中空糸膜巻き上げ体に存在する中空糸膜総容積(中空糸膜外径基準)を中空糸膜巻き上げ体の容積で割って求めた。
充填率(%)=π×(中空糸膜の外径)2/4(m2)×中空糸膜の総全長(m)/中空糸膜巻上げ体容積(m3)×100%
なお、中空糸膜巻き上げ体容積=π×(DO)2×(LE)
中空糸膜の総全長=平均有効長×中空糸膜本数
中空糸膜エレメント1本を圧力容器に装填して中空糸膜モジュールを作成し、中空糸膜のそれぞれの開口部に連通するノズルのうち、一方のノズルより塩化ナトリウム濃度0.2g/Lの淡水を供給ポンプで供給し、他方のノズルから淡水を流出させた。一方、塩化ナトリウム濃度70g/Lの高濃度水溶液を中空糸膜の外側に連通する多孔分配管に供給ポンプで供給し、中空糸膜の外側を通過させた後、中空糸膜集合体の外側に連通する圧力容器の側面に配置するノズルから流出させ、流量調整バルブで、圧力と流量を調整する。高濃度水溶液の供給圧力をPDS1(MPa)、供給流量をQDS1(L/min)、高濃度水溶液の排出水量をQDS2(L/min)、淡水の供給流量をQFS1(L/min)、淡水の流出流量をQFS2(L/min)、淡水の流出圧力をPFS2(kPa)とした場合、その条件での高濃度水溶液の流量増分(QDS2-QDS1)をモジュールの透過水量として測定した。温度は25℃に調整した。
PDS1=2.2MPa
PFS2=10kPa以下
QDS1/(QDS2-QDS1)=2
QFS2/(QDS2-QDS1)=0.1
ただし、淡水の入口圧力は0.1MPaとし、0.1MPaを越える場合は、0.1MPaとなるようにQFS1を設定した。
なお、比較例1(従来タイプROモジュール)の透過水量を基準として、各実施例の透過水量増加率を下記式にしたがって算出した。
例)透過水量増加率(%)=(実施例1の透過水量―比較例1の透過水量)/比較例1の透過水量×100
高濃度水溶液の代わりに耐汚染性測定用の高汚染模擬海水を用いた以外は上記の透水量の測定と同様の運転条件で連続運転を実施し、高濃度水溶液の供給圧力(PDS1)と出口圧力(PDS2)との差圧(PDS1-PDS2)の推移等を測定し、100時間後の差圧と高濃度水溶液の場合の差圧との比を差圧上昇率として、中空糸膜エレメントの汚染状況を測定した。なお、この高汚染模擬海水の組成は、逆浸透膜処理水に塩化ナトリウム濃度70g/L、アルギン酸ナトリウム0.8g/L、コロイダルシリカ(PL-7)90mg-SiO2/L、塩化第二鉄六水和物10mg/Lからなる。
三酢酸セルロース(CTA、ダイセル化学工業社、LT35)41重量%、N-メチル-2-ピロリドン(NMP、三菱化学社)50重量%、エチレングリコール(EG、三菱化学社)8.7重量%、安息香酸(ナカライテスク社)0.3重量%を180℃で均一に溶解して製膜原液を得た。得られた製膜原液を減圧下で脱泡した後、アーク型(三分割)ノズルより163℃で外気と遮断された空間中に吐出し、空間時間0.03秒を経て、NMP/EG/水=4.25/0.75/95からなる12℃の凝固浴に浸漬した。引続き、多段傾斜桶水洗方式で中空糸膜の洗浄を行い、湿潤状態のまま振り落した。得られた中空糸膜を90℃の水に浸漬し、20分間熱水処理を行った。
得られた中空糸膜は、内径が85μm、外径が175μmであった。
得られた中空糸膜エレメントは、中空糸膜巻き上げ体の最外層から巻き上げ体の厚みの3/4までの部分(外層部)において、エレメント長あたりのワインド数が0.5であり、それ以外の部分(内層部)のエレメント長あたりのワインド数が2.0であり、長さ約70cm、外径130mm、中空糸膜の充填率51%、膜面積は67m2であった。この中空糸膜エレメントを圧力容器に装填してモジュールとして各種試験を行なった。その結果を中空糸膜とエレメントの詳細とともに表1に示す。
実施例1と同様の中空糸膜を用いて、外層部のワインド数を1.0に変更した以外は、実施例1と同様にして中空糸膜エレメントを作成した。この中空糸膜エレメントを圧力容器に装填してモジュールとして各種試験を行なった。その結果を中空糸膜とエレメントの詳細とともに表1に示す。
実施例1と同様の中空糸膜を用いて、外層部のワインド数を1.5に変更した以外は、実施例1と同様にして中空糸膜エレメントを作成した。この中空糸膜エレメントを圧力容器に装填してモジュールとして各種試験を行なった。その結果を中空糸膜とエレメントの詳細とともに表1に示す。
実施例1と同様の中空糸膜を用いて、外層部(中空糸膜巻上げ体の最外層から巻き上げ体の厚みの1/8までの部分)において、エレメント長あたりのワインド数を1.0、それ以外の部分(内層部)のワインド数を2.0に変更した以外は、実施例1と同様にして中空糸膜エレメントを作成した。この中空糸膜エレメントを圧力容器に装填してモジュールとして各種試験を行なった。その結果を中空糸膜とエレメントの詳細とともに表1に示す。
実施例1と同様の中空糸膜を用いて、エレメントの外径を420mm、外層部(中空糸膜巻上げ体の最外層から巻き上げ体の厚みの3/4までの部分)において、エレメント長あたりのワインド数を1.0、それ以外の部分(内層部)のワインド数を2.0に変更した以外は、実施例1と同様にして中空糸膜エレメントを作成した。この中空糸膜エレメントを圧力容器に装填してモジュールとして各種試験を行なった。その結果を中空糸膜とエレメントの詳細とともに表1に示す。
実施例1と同様の中空糸膜を用いて、内層部も外層部もワインド数を2.0に変更した以外は、実施例1と同様にして中空糸膜エレメントを作成した。この中空糸膜エレメントを圧力容器に装填してモジュールとして各種試験を行なった。その結果を中空糸膜とエレメントの詳細とともに表1に示す。
実施例1と同様の中空糸膜を用いて、外層部のワインド数を0.25に変更した以外は、実施例1と同様にして中空糸膜エレメントを作成した。この中空糸膜エレメントを圧力容器に装填してモジュールとして各種試験を行なった。その結果を中空糸膜とエレメントの詳細とともに表1に示す。
実施例1と同様の中空糸膜を用いて、外層部(中空糸膜巻上げ体の最外層から巻き上げ体の厚みの1/10までの部分)のワインド数を1.0、それ以外の部分(内層部)のワインド数を2.0に変更した以外は、実施例1と同様にして中空糸膜エレメントを作成した。この中空糸膜エレメントを圧力容器に装填してモジュールとして各種試験を行なった。その結果を中空糸膜とエレメントの詳細とともに表1に示す。
テレフタル酸ジクロリド及び70mol%の4,4’-ジアミノジフェニルスルホン、30mol%のピペラジンより低温溶液重合法で得た共重合ポリアミドを精製した後、このもの36重量部をCaCl2 4重量部(ポリマーに対して)及びジグリセリン3.6重量部(ポリマーに対して)を含むジメチルアセトアミド溶液に80℃で溶解し、製膜溶液とした。この溶液を脱泡した後、3分割ノズルより吐出し、空中走行部を経て4~6℃に冷却した凝固液中に浸漬し中空糸膜を得た。次いで得られた中空糸膜を水洗した後、75~85℃で30分間熱処理した。得られた中空糸膜は、内径100μm、外径200μmであった。
得られた中空糸膜エレメントの外層部(中空糸膜巻上げ体の最外層から巻き上げ体の厚みの3/4までの部分)のワインド数は1.0、それ以外の部分(内層部)のワインド数は2.0、長さ約70cm、外径130mm、中空糸膜の充填率51%、膜面積は58m2であった。この中空糸膜エレメントを圧力容器に装填してモジュールとして各種試験を行なった。その結果を中空糸膜とエレメントの詳細とともに表1に示す。
3,3’-ジスルホ-4,4’-ジクロロジフェニルスルホン2ナトリウム塩(S-DCDPS)11.5mol%、2,6-ジクロロベンゾニトリル(DCBN)38.5mol%、4,4’-ビフェノール50mol%を重合して得たスルホン化ポリアリールエーテルスルホン(SPN-23)を、予め110℃12時間乾燥した後、80重量部量りとり、続いてNMP108重量部、EG12重量部を170℃で攪拌溶解して製膜溶液を得た。
この製膜溶液を150℃に保ちチューブインオリフィス型ノズルから、EGを内液として吐出した。エアギャップ長を20mmとし、濃度3.5重量%の塩水からなる凝固浴に浸漬した。引続き、多段傾斜桶水洗方式で中空糸膜の洗浄を行い、湿潤状態のまま振り落した。得られた中空糸膜を濃度14.5重量%の塩水に浸漬させ、温度98℃、時間20分の条件でアニール処理を行った。
得られた中空糸膜エレメントの外層部(中空糸膜巻上げ体の最外層から巻き上げ体の厚みの3/4までの部分)のワインド数は1.0、それ以外の部分(内層部)のワインド数は2.0、長さ約70cm、外径130mm、中空糸膜の充填率51%、膜面積は71m2であった。この中空糸膜エレメントを圧力容器に装填してモジュールとして各種試験を行なった。その結果を中空糸膜とエレメントの詳細とともに表1に示す。
Claims (7)
- 多孔分配管の周りに中空糸膜を螺旋状に巻回することにより中空糸膜を交差状に配置した中空糸膜巻上げ体の両端部を開口させた両端開口型の中空糸膜エレメントであって、
a)前記中空糸膜巻上げ体の最外層から巻き上げ体の厚みの少なくとも1/8までの範囲において、エレメント長あたりのワインド数を0.33~1.75とし、
b)前記中空糸膜巻き上げ体の最内層から巻き上げ体の厚みの少なくとも1/4までの範囲において、エレメント長あたりのワインド数を1.75超としたことを特徴とする正浸透用中空糸膜エレメント。 - 前記中空糸膜巻上げ体の最外層から巻き上げ体の厚みの最大3/4までの範囲において、エレメント長あたりのワインド数を0.33~1.75としたことを特徴とする請求項1に記載の正浸透用中空糸膜エレメント。
- 前記エレメントの外径が130mm以上であることを特徴とする請求項1または2に記載の正浸透用中空糸膜エレメント。
- 中空糸膜が、酢酸セルロース系樹脂、ポリアミド系樹脂、及びスルホン化ポリスルホン系樹脂からなる群から選ばれる1種以上の樹脂からなることを特徴とする請求項1~3のいずれかに記載の正浸透用中空糸膜エレメント。
- 中空糸膜の外径が160~270μmであることを特徴とする請求項1~4のいずれかに記載の正浸透用中空糸膜エレメント。
- 中空糸膜巻上げ体の外径が130~420mm、長さが0.2~1.6mであることを特徴とする請求項1~5のいずれかに記載の正浸透用中空糸膜エレメント。
- 請求項1~6のいずれかに記載の正浸透用中空糸膜エレメント1本以上を容器に装填したことを特徴とする正浸透用中空糸膜モジュール。
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US (1) | US10029212B2 (ja) |
EP (1) | EP3061519B1 (ja) |
JP (1) | JP6222237B2 (ja) |
DK (1) | DK3061519T3 (ja) |
ES (1) | ES2871870T3 (ja) |
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US11020705B2 (en) * | 2013-12-27 | 2021-06-01 | Toray Advanced Materials Korea Inc. | Porous outflow pipe for forward osmosis or pressure-retarded osmosis, and forward osmosis or pressure-retarded osmosis module comprising same |
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CN108136333A (zh) * | 2015-08-31 | 2018-06-08 | 波里费拉公司 | 具有经加压出料流的水净化系统及方法 |
JP6972737B2 (ja) * | 2017-07-28 | 2021-11-24 | 東洋紡株式会社 | 中空糸膜モジュール |
CN112156658B (zh) * | 2020-10-13 | 2022-04-01 | 上海工程技术大学 | 一种中空纤维膜的制备装置 |
CN112472361B (zh) * | 2020-12-02 | 2021-08-27 | 武汉杨森生物技术有限公司 | 一种抗弯折人工血管及其制备方法 |
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- 2014-10-21 JP JP2015543861A patent/JP6222237B2/ja active Active
- 2014-10-21 WO PCT/JP2014/077910 patent/WO2015060286A1/ja active Application Filing
- 2014-10-21 EP EP14855020.5A patent/EP3061519B1/en active Active
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JPS5337183A (en) * | 1976-09-17 | 1978-04-06 | Toyobo Co Ltd | Preparation of assembled body of hollow filament |
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Also Published As
Publication number | Publication date |
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US10029212B2 (en) | 2018-07-24 |
ES2871870T3 (es) | 2021-11-02 |
EP3061519A4 (en) | 2017-06-14 |
SA516370621B1 (ar) | 2017-05-23 |
US20160207000A1 (en) | 2016-07-21 |
EP3061519A1 (en) | 2016-08-31 |
EP3061519B1 (en) | 2021-04-21 |
JP6222237B2 (ja) | 2017-11-01 |
DK3061519T3 (da) | 2021-07-05 |
JPWO2015060286A1 (ja) | 2017-03-09 |
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