Rechargeable pore-filling hollow fiber membrane for water vapor separation, manufacturing method and apparatus thereof

Abstract

The present specification provides a pore-refilled hollow fiber membrane for water separation comprising a newly manufactured or reused hollow fiber membrane having two or more pores, a first material having a hydroxyl (-OH) group or a second material having an amine (-NH2) group, and a double crosslinking agent condensed with the first or second material, mixed with a viscous material and impregnated into each of the pores, a hydrophilic filler, a method for manufacturing the same, and an apparatus including the same.

Description

Technology Field

[0001] The present specification relates to a porous refilled hollow fiber membrane for water separation, a method for manufacturing the same, and an apparatus including the same. Background Technology

[0002] White smoke emitted from power plant stacks or cooling towers is perceived as a major concern due to aesthetic and environmental issues, leading to growing anxiety among citizens.

[0003] White plume is a phenomenon in which a large amount of cooling water evaporates from a cooling tower, meets outside cold air to become supersaturated steam, and appears like white smoke. Since it is discharged in the largest quantities from the water flow of power plants, it also causes water shortage problems. If it were possible to recover some of the water vapor—the white plume—that is discharged and disappears outside the cooling tower, not only the white plume problem but also the water shortage problem could be solved. Accordingly, many researchers are actively conducting research on dehumidification technologies to recover water vapor.

[0004] Common dehumidification methods include condensers and desiccant drying. Compared to other methods, condensation is relatively dirty and causes corrosion, while desiccant drying is difficult to operate as a continuous process because it requires regeneration. Furthermore, since both methods consume a significant amount of energy, the development of new technologies capable of reducing energy consumption is necessary. The problem to be solved

[0005] The present embodiment provides a pore-refilling hollow fiber membrane for water separation that separates water using a hollow fiber membrane containing pores at a low cost and regenerates the pores by refilling them, a method for manufacturing the same, and an apparatus thereof. means of solving the problem

[0006] A pore-refilled hollow fiber membrane for water separation according to one embodiment comprises a newly manufactured or reused hollow fiber membrane having two or more pores, a first material having a hydroxyl (-OH) group or a second material having an amine (-NH2) group, and a double crosslinking agent condensed with the first material or the second material, mixed with a viscous material and impregnated into each of the pores with a hydrophilic filler.

[0007] A method for manufacturing a pore-refilled hollow fiber membrane for water separation according to another embodiment comprises: a first step of newly manufacturing or reusing a hollow fiber membrane containing two or more pores; a first step of filling each of the pores with a mixture of a liquid viscous substance mixed with a first substance having a hydroxyl (-OH) group or a second substance having an amine (-NH2) group and a double crosslinking agent that crosslinks with the first substance or the second substance; and a third step of heat-treating the hollow fiber membrane to carry out condensation polymerization of the first substance or the second substance and the double crosslinking agent to impregnate the pores of the hollow fiber membrane with a hydrophilic filler.

[0008] A device according to another embodiment includes a pore-refilled hollow fiber membrane for moisture separation. In this case, the device may be a cooling tower or a building air conditioning system in which the pore-refilled hollow fiber membrane for moisture separation is disposed at the bottom of an exhaust fan. Effects of the invention

[0009] The pore-refilling hollow fiber membrane for water separation and the method for manufacturing the same and the apparatus according to the present embodiment can separate water using a hollow fiber membrane containing pores at a low cost and regenerate by refilling the pores. Brief explanation of the drawing

[0010] FIG. 1 is a schematic diagram of a porous refilled hollow fiber membrane for moisture separation according to one embodiment. FIGS. 2a and 2b are process diagrams of a method for manufacturing a pore-refilled hollow fiber membrane for moisture separation according to one embodiment. Figure 3 is an SEM image of an HDPE hollow fiber membrane according to a manufacturing example. Figure 4 shows the pore size distribution of an HDPE hollow fiber membrane according to the manufacturing example of Figure 3. Figure 5 illustrates the contact angle of a hollow fiber membrane according to the manufacturing example of Figure 3. Figure 6 shows the thermogravimetric analysis results of the hollow fiber membrane according to the manufacturing example of Figure 3. FIG. 7 is a cross-sectional view of a cooling tower according to another embodiment. Specific details for implementing the invention

[0011] Hereinafter, some embodiments of the present disclosure will be described in detail with reference to the exemplary drawings. In assigning reference numerals to the components of each drawing, the same components may have the same reference numeral as much as possible, even if they are shown in different drawings. Furthermore, in describing the embodiments, if it is determined that a detailed description of related known components or functions may obscure the essence of the technical concept, such detailed description may be omitted. Where terms such as "comprising," "having," or "consisting of" are used in this specification, other parts may be added unless "only" is used. Where a component is expressed in the singular, it may include a plural unless otherwise specified.

[0012] Additionally, terms such as first, second, A, B, (a), (b), etc., may be used to describe the components of the present disclosure. These terms are used merely to distinguish the components from other components, and the nature, order, sequence, or number of the components are not limited by such terms.

[0013] In describing the positional relationship of components, where it is stated that two or more components are "connected," "combined," or "joined," it should be understood that while the two or more components may be directly "connected," "combined," or "joined," they may also be "connected," "combined," or "joined" with other components "intervened." Here, the other components may be included in one or more of the two or more components that are "connected," "combined," or "joined" with one another.

[0014] In describing the temporal flow relationship regarding components, methods of operation, or methods of production, for example, when the temporal or sequential relationship is described using "after," "following," "next," or "before," it may include cases where the relationship is not continuous unless "immediately" or "directly" is used.

[0015] Meanwhile, where numerical values ​​or corresponding information regarding a component (e.g., levels, etc.) are mentioned, even without separate explicit notation, the numerical values ​​or corresponding information may be interpreted as including a range of error that may occur due to various factors (e.g., process factors, internal or external shocks, noise, etc.).

[0016] As mentioned above, research on dehumidification technology is actively being conducted to recover a portion of the water vapor, specifically the white smoke, that is discharged and disappears outside the cooling tower.

[0017] Common dehumidification methods include condensers and desiccant drying. Compared to other methods, condensation is relatively dirty and causes corrosion, while desiccant drying is difficult to operate as a continuous process because it requires regeneration. Furthermore, since both methods consume a significant amount of energy, the development of new technologies capable of reducing energy consumption is necessary.

[0018] Recently, research on dehumidification using hollow fiber membranes has been underway. When a vacuum is applied inside a hydrophilic, non-porous membrane, external moisture permeates into the membrane and is separated due to the concentration and pressure differences between the inside and outside of the membrane. Since membrane technology selectively separates only moisture (dehumidification) without temperature changes (isothermal), it consumes less energy compared to other technologies. Furthermore, because the recovered water is as clean as distilled water, it can be utilized in high-value-added industries. In addition, membrane technology offers wide applicability and allows for perfect installation, as it can be used not only to reduce white plume in cooling towers but also as a dehumidification device for clean rooms and dressing rooms.

[0019] Since moisture separation membranes must selectively separate only moisture from the air, they must be manufactured to be non-porous and possess hydrophilicity. Furthermore, for commercial use, they must be inexpensive. To this end, research is actively underway to fabricate thin film composite membranes (TFCs) by utilizing inexpensive hollow fiber ultrafiltration membranes for water treatment as a support and introducing a selective layer by thinly coating the surface of the support with a hydrophilic material. Since the selective layer serves to block the membrane's pores and enhance hydrophilicity, the membrane's moisture permeability and selectivity vary depending on the selective layer. Coating is generally carried out using dipping and interfacial polymerization methods.

[0020] Since the coating introduced on the membrane surface generally has a thickness of tens to hundreds of nanometers, it is difficult to form a dense film with the coating if pores larger than these exist on the membrane surface. If large pores exist on the membrane surface, not only moisture but also air composed of nitrogen and oxygen passes through, preventing selective separation.

[0021] However, since it is very difficult to control the pore size uniformly during the manufacturing process, the types of hollow fiber membranes used as supports for water separation membranes are inevitably limited. For this reason, hollow fiber membranes with relatively small and uniform pore sizes must be used as supports. However, if a coating technology is developed that allows the use of hollow fiber membranes as supports—which have larger pores and a wider pore size distribution but are cheaper—the value of their application in the field of water separation using membranes will increase even further.

[0022] The present specification provides a technology for coating a hollow fiber membrane with large pores using a rechargeable pore-filling method.

[0023] FIG. 1 is a schematic diagram of a porous refilled hollow fiber membrane for moisture separation according to one embodiment.

[0024] Referring to FIG. 1, a pore-refilled hollow fiber membrane (100) for water separation according to one embodiment comprises a newly manufactured or reused hollow fiber membrane (110) having two or more pores (112) and a hydrophilic filler (120) in which a double-crosslinker, which is condensed with the first or second material and mixed with a viscous material, is impregnated into each of the pores (112).

[0025] As described below with reference to FIG. 2, the hollow fiber membrane (110) may be a newly manufactured hollow fiber membrane or a hollow fiber membrane from which the filler (120) has been removed from a hollow fiber membrane impregnated with the filler (120) and then reused.

[0026] A hollow fiber membrane (110) is used as a substrate. The hollow fiber membrane (110) may be a thin film composite membrane (TFC) manufactured using various known polymers. For example, the hollow fiber membrane (110) may be made of HDPE (high density polyethylene).

[0027] The double crosslinking agent is a liquid viscous substance that is generally used as a pore stabilizer after manufacturing a hollow fiber membrane. The hollow fiber membrane (110) is used for water treatment and gas separation only if pores (112) are present, because without the stabilizer, the hollow fiber membrane (110) dries out and the pores (112) close.

[0028] The double crosslinking agent can crosslink with the hydroxyl (-OH) or amine (-NH2) groups of other materials. That is, materials containing hydroxyl (-OH) groups, amine (-NH2) groups, etc. can undergo condensation polymerization with the double crosslinking agent and can be used for filling the pores of the hollow fiber membrane (110).

[0029] The first material having a hydroxyl (-OH) group is one of PVA (polyvinyl alcohol), PEG (polyethylene glycol), or cellulose, and the second material having an amine (-NH2) group can be one of PEI (polyethyleneimine), gelatin, chitosan, or collagen. As the first material having a hydroxyl (-OH) group, PVA has the advantages of good polymerization, excellent hydrophilicity, and low cost because it has many hydroxyl (-OH) groups per repeat unit. As the second material having an amine (-NH2) group, PEI has the advantage of having many amine (-NH2) groups per repeat unit.

[0030] The double crosslinking agent is glutaraldehyde (GA), and the viscous agent may be glycerol or polyethylene glycol (PEG) with a molecular weight of 100 to 1000. Glycerol or polyethylene glycol (PEG) with a molecular weight of 100 to 1000 is a liquid viscous agent and can generally be used as a pore stabilizer after manufacturing a hollow fiber membrane (110).

[0031] Glycerol is a safe and inexpensive substance used in the food industry (humectants, solvents, sweeteners, etc.), cosmetics (moisturizers), and hand sanitizers (moisturizers).

[0032] Polyethylene glycol (PEG) is a substance similar in nature to glycerol. The viscosity of PEG varies depending on its molecular weight. That is, since PEG1000, which has a molecular weight exceeding 1000, is in a solid state, PEG with a molecular weight ranging from 100 to 1000 (e.g., PEG200, PEG300, PEG400, PEG600) can be used as a double crosslinking agent.

[0033] When a water drop is dropped onto the surface (114) of a hollow fiber membrane (110) impregnated with a filler (120) in the pore (112), the contact angle at which the water drop spreads is less than 10 degrees, and when a water drop is dropped onto the surface (114) of a hollow fiber membrane (110) from which the filler (120) has been removed in the pore (112), the contact angle at which the water drop spreads may be 60 degrees or more, for example, 70 degrees.

[0034] The contact angle is the value obtained by dropping a small drop of water onto the surface (114) of the hollow fiber membrane (110) and measuring the angle of the water drop. As a comparative example, the surface of a lotus flower has small hydrophobic protrusions, so the water drop does not spread and is hydrophobic. Similarly, the hollow fiber membrane (110) is impregnated with the aforementioned filler (120), and since these impregnated materials are very hydrophilic, when a water drop is dropped onto the surface (114) of the hollow fiber membrane (110), it spreads immediately. In other words, this means that the hollow fiber membrane (110) is very hydrophilic.

[0035] In other words, the protruding part above is a water droplet intentionally dropped to measure the contact angle, and the surface (114) of the hollow fiber membrane (110) in which the filler (120) is impregnated into the pores (112) is hydrophilic, so the water droplet spreads out and the contact angle is less than 10 degrees, and when washed, the hydrophilic filler (120) is washed away by water and the hydrophilicity weakens, so the contact angle can go up to 60 degrees or more, for example, about 70 degrees.

[0036] In the following manufacturing examples, the first material is PVA, the second material is PEI (polyethyleneimine), the crosslinking agent is glutaraldehyde (GA), and the viscous material is glycerol, but is not limited thereto.

[0037] For example, glycerol is preferably 15 to 60 wt% relative to the total solution, and more preferably 30 to 60 wt%. If the glycerol content is too low, the ratio of the filler (120) relative to the total solution is low, so the pores (112) of the hollow fiber membrane (110) may not be filled, and if the content is too high, the viscosity increases, making it difficult to fill the pores (112).

[0038] PVC is preferably 0.5 to 3 wt% relative to the total solution, and more preferably 0.5 to 1.5 wt%. If the PVA content is too low, the degree of crosslinking decreases, and as the viscosity decreases after heat treatment, leakage of the filler (120) may occur, and if the content is too high, crosslinking occurs excessively, and the strands of the hollow fiber membrane (110) may stick together.

[0039] FIGS. 2a and 2b are process diagrams of a method for manufacturing a pore-refilled hollow fiber membrane for moisture separation according to one embodiment.

[0040] Referring to FIG. 2a, a method (200A) for manufacturing a pore-refilling hollow fiber membrane for water separation according to another embodiment comprises a first step (a) of newly manufacturing or reusing a hollow fiber membrane (110) having two or more pores (112); a first step (b) of filling each of the pores (112) with a mixture (122) in which a liquid viscous substance is mixed with a first substance having a hydroxyl (-OH) group or a second substance having an amine (-NH2) group and a double crosslinking agent that crosslinks with the first substance or the second substance; and a third step of heat-treating the hollow fiber membrane (110) to proceed with condensation polymerization of the first substance or the second substance and the double crosslinking agent to impregnate the pores (112) of the hollow fiber membrane (110) with a hydrophilic filler (120).

[0041] In the first step (a), as illustrated in FIG. 2b, in the method (200B) for manufacturing a pore-refilled hollow fiber membrane for water separation according to another embodiment, when the hollow fiber membrane (110) is reused, the hollow fiber membrane (110) from which the hydrophilic filler (120) has been removed by washing with water can be reused.

[0042] The double crosslinking agent is a liquid viscous substance that is generally used as a pore stabilizer after manufacturing a hollow fiber membrane. The hollow fiber membrane (110) is used for water treatment and gas separation only if pores (112) are present, because without the stabilizer, the hollow fiber membrane (110) dries out and the pores (112) close.

[0043] The double crosslinking agent can crosslink with the hydroxyl (-OH) or amine (-NH2) groups of other materials. That is, materials containing hydroxyl (-OH) groups, amine (-NH2) groups, etc. can undergo condensation polymerization with the double crosslinking agent and can be used for filling the pores of the hollow fiber membrane (110).

[0044] The first material having a hydroxyl (-OH) group is one of PVA, PEG, and cellulose, and the second material having an amine (-NH2) group may be one of PEI, gelatin, chitosan, and collagen.

[0045] The double crosslinking agent is glutaraldehyde, and the viscous agent may be glycerol or PEG with a molecular weight of 100 to 1000. Glycerol or PEG with a molecular weight of 100 to 1000 is a liquid viscous agent and can generally be used as a pore stabilizer after manufacturing a hollow fiber membrane (110).

[0046] As described above, when a water drop is dropped on the surface (114) of a hollow fiber membrane (110) impregnated with a filler (120) in the pore (112), the contact angle of the water drop is less than 10 degrees, and when a water drop is dropped on the surface (114) of a hollow fiber membrane (110) from which the filler (120) has been removed in the pore (112), the contact angle of the water drop is 60 degrees or more, for example, 70 degrees.

[0047] In the following manufacturing examples, the first substance is PVA, the second substance is PEI, the crosslinking agent is glutaraldehyde, and the viscous agent is glycerol, but this is not limited thereto.

[0048] In step 2 (b), glycerol, polyvinyl alcohol (PVA), glutaaldehyde (GA), etc. can be used as the hydrophilic filler (120) for coating.

[0049] As described above, glycerol is a viscous liquid that has many hydroxyl (-OH) groups, making it highly hydrophilic and a material that can be easily introduced into the pores (112). After dissolving glycerol, PVA, GA, etc. in water, if the mixture (122) is filled into the pores (112) using a pump, the pores (112) are filled and a dense membrane is formed. However, since glycerol is a liquid, it can escape into the interior when a vacuum is applied inside the hollow fiber membrane (110), so the viscosity must be increased to prevent this.

[0050] In the third step (c), a liquid solution (122) in which glycerol is mixed with PVA and GA is filled into the pores, and then the PVA and GA are cross-linked through heat treatment to create a gel-like viscous body. For example, a hollow fiber membrane (110) is placed in an oven maintained at a certain temperature, for example, 70 degrees, and heat treatment is carried out for a certain period of time so that the PVA and GA are cross-linked with each other.

[0051] If the pores (112) are filled with a solid material, the mobility in the free space of the hollow fiber membrane (110) is low, which reduces permeability; however, in a gel state, which is a viscous material, the mobility is superior to that of the solid state, so permeability can be increased. Of course, since the glycerol / PVA / GA crosslinking material is a viscous material, if the hollow fiber membrane (110) is washed with warm water, the filler (120) may come out of the hollow fiber membrane (110). However, if it is used as an indoor dehumidifier without contact with water, these problems can be solved.

[0052] In addition, as shown in FIG. 2b, when the hollow fiber membrane (110) that serves as a support is recycled, it can be rechargeable by washing the hollow fiber membrane (110) by impregnating it with warm water and then filling it with another filler (120).

[0053] The regenerable porous impregnated membrane (100) can, first, densify a membrane with large pores, second, regenerate (recharge) when the coating film is contaminated, and third, adjust the degree of densification according to the application.

[0054] Hereinafter, with reference to the drawings, an example of manufacturing a pore-refilled hollow fiber membrane for moisture separation according to another embodiment described above and the results of confirming the characteristics of the manufactured pore-refilled hollow fiber membrane for moisture separation will be explained.

[0055] Figure 3 is an SEM image of an HDPE hollow fiber membrane according to a manufacturing example. Figure 4 shows the pore size distribution of the HDPE hollow fiber membrane according to the manufacturing example of Figure 3. Figure 5 illustrates the contact angle of the hollow fiber membrane according to the manufacturing example of Figure 3. Figures 6 and 7 show the thermogravimetric analysis results of the hollow fiber membrane according to the manufacturing example of Figure 3.

[0056] [Preparation Example]

[0057] HDPE (high density polyethylene) hollow fiber membranes (110) used for water treatment were purchased, and as shown in FIGS. 3 and 4, it was confirmed that these hollow fiber membranes (110) have pore sizes of tens to hundreds of nanometers.

[0058] The impregnation mixture (122) was prepared by mixing 50 wt% glycerol, 1 wt% PVA, 0.5 wt% GA, 0.5 wt% HCl, and 48 wt% water relative to the total solution.

[0059] After immersing the hollow fiber membrane (110) in a solution, if the inside of the hollow fiber membrane (110) is depressurized using a pump, the mixture (122) outside the hollow fiber membrane (110) enters the inside due to the pressure difference and fills the pores (112) of the hollow fiber membrane (110).

[0060] After impregnating the mixture into the pores (112) of the hollow fiber membrane (110) using a pump for a certain period of time, the hollow fiber membrane (110) is shaken to remove the mixture (122) remaining on the outside.

[0061] A hollow fiber membrane (110) is placed in an oven maintained at 70 degrees and heat-treated for 30 minutes to allow PVA and GA to cross-link with each other. Before heat treatment, it is a low-viscosity solution, but after heat treatment, as PVA and GA are cross-linked, it becomes a porous impregnated filler (120) with increased viscosity.

[0062] The contact angle resulting from coating an HDPE hollow fiber membrane (110) with a 50 wt% glycerol / 1 wt% PVA / 0.5 wt% GA / 0.5 wt% HCl mixture (containing H2O) and then washing it with tap water is shown in FIG. 5.

[0063] As shown in FIG. 5, after washing, the hollow fiber membrane (110) was dried by storing it at room temperature for one week. After being coated with a filler (120), the contact angle was found to be hydrophilic with a contact angle of 10 degrees or less, and after washing, the contact angle increased again and showed similar values ​​even when coating / washing was repeated. This indicates that refilling is working well.

[0064] The thermal properties of the membrane according to coating / washing were evaluated using a thermogravimetric analyzer (TGA).

[0065] After coating, it was confirmed that 65 to 70 wt% of the filler was well contained regardless of the number of coatings, and after washing, it was confirmed that about 15 wt% of water was contained. It is believed that the water inside the pores (112) was measured because the hollow fiber membrane (110) was not dried at a high temperature or under vacuum after washing.

[0066] Figure 6 shows the results of the thermogravimetric analysis of the membrane (100), including the moisture permeability and selectivity of the membrane measured at a temperature of 30 degrees and a relative humidity of 80%. Even as coating progressed, the moisture permeability remained constant at 2000–2050 GPUs and the selectivity at 200–220, indicating that the filler was well filled with the number of coating cycles. In other words, it was found that refilling was possible. For the washed membrane (110), the moisture permeability and selectivity could not be measured because no pressure was applied due to leakage caused by the loss of the filler (120).

[0067] Meanwhile, in the glycerol / PVA / GA mixture, the content of PVA and GA is very low, so glycerol accounts for most of the content. Based on 50G / 1PVA / 0.5GA containing 50wt% glycerol, glycerol / PVA / GA accounts for 51.5wt%, and the remainder is water.

[0068] That is, after filling the pores (112) of the hollow fiber membrane (110) with the filler (120), if time passes or a vacuum is applied inside, only low-viscosity water will come out. That is, about 50% of the viscous material will remain in the pores (112) of the hollow fiber membrane (110).

[0069] The pore-refilled hollow fiber membrane (110) for water separation manufactured by the example of manufacturing a pore-refilled hollow fiber membrane for water separation according to the other embodiment described above has the following characteristics.

[0070] - A hollow fiber membrane (110) with large pores (112) and a wide pore distribution can be made into a dense membrane for moisture separation by impregnating the pores using a filler (120).

[0071] - In order to impregnate the pores (112) with the filler (120), the viscosity must be low. Since the glycerol / PVA / GA / HCl / H2O mixture (122) does not undergo cross-linking when used before heat treatment or within 1 hour of making the solution, the pores (112) can be impregnated in a low-viscosity solution state.

[0072] - In order to improve impregnation, the temperature of the mixture (122) is raised (up to 50 degrees) before impregnation, so at temperatures above 50 degrees, HCl evaporates quickly, which can lower the quality and cause cross-linking to proceed quickly.

[0073] - When refilling due to leakage or contamination of the filler (120) or when reusing the hollow fiber membrane (110) which is the support, the hollow fiber membrane (110) can be reused by immersing it in water to remove the filler (120).

[0074] A device according to another embodiment includes a pore-refilled hollow fiber membrane (100) for moisture separation. In this case, the device may be a cooling tower or a building air conditioning system in which the pore-refilled hollow fiber membrane (100) for moisture separation is disposed at the bottom of an exhaust fan.

[0075] In addition, the pore-refilled hollow fiber membrane (100) for moisture separation can be used for various purposes such as the following.

[0076] - A pore-refilled hollow fiber membrane (100) for moisture separation can be applied to a building air conditioner or indoor dehumidifier to lower the indoor relative humidity to an appropriate level, thereby creating a comfortable indoor air environment.

[0077] Since the dressing room is a closed space, ventilation is difficult, and mold can grow on the walls, ceiling corners, and clothes due to humid air. To prevent this, a dehumidification process is essential, and if a moisture-separating porous refilled hollow fiber membrane (100) is applied to such a dressing room to perform dehumidification with less energy, the dressing room can be kept comfortable without the burden of electricity costs.

[0078] - An air conditioning dehumidification system is essential for preventing internal condensation and maintaining optimal humidity (50~60%). After applying a pore-refilled hollow fiber membrane (100) for moisture separation to the armory, the optimal humidity of the armory can be maintained by controlling the amount of dehumidification by adjusting the vacuum pressure intensity.

[0079] - The optimal humidity condition for a typical cleanroom is 50~60%, and dry dehumidification (silica gel rotor) is used when the humidity is 40% or lower, and cooling dehumidification (cooling coil) is used when the humidity is 50% or higher, but as described above, there is a disadvantage of high energy consumption. By applying a porous refilled hollow fiber membrane (100) for moisture separation to the cleanroom process, it is possible to reduce the cost of the existing cleanroom dehumidification process.

[0080] In addition, the pore-refilled hollow fiber membrane (100) for moisture separation can also be applied to pharmaceutical storage, agricultural product / food storage, and workplaces requiring humidity control (computer room, machine room, broadcasting room, warehouse, etc.).

[0081] - The pore-refilled hollow fiber membrane (100) for moisture separation can be used for white smoke reduction.

[0082] - Water condensed by passing through the pore-refilled hollow fiber membrane (100) for water separation is as clean as water obtained through the NF membrane, so it can be reused for industrial water as well as for high value-added industries.

[0083] In the following description, with reference to FIG. 8, a cooling tower having a pore-refilled hollow fiber membrane (100) for moisture separation placed at the bottom of the exhaust fan is described as an example, but is not limited thereto.

[0084] FIG. 7 is a cross-sectional view of a cooling tower according to another embodiment.

[0085] Referring to FIG. 7, a cooling tower (300) according to another embodiment is a counter-flow cooling tower that includes an eliminator (320) and an exhaust fan (330) inside a main body (310).

[0086] The pore-refilled hollow fiber membrane (100) for water separation described with reference to FIGS. 1 to 6 is placed in the exhaust fan (330) between the eliminator (320) and the exhaust fan (330). The membrane (110) can recover clean water by condensing water vapor from the white smoke that passes through the eliminator (320) and is discharged to the outside through the exhaust fan (330). The water condensed by the membrane (110) can be transferred to an external water tank through a water drain pipe (not shown) and used as industrial water.

[0087] The membrane (110) can be manufactured into a membrane module by weaving hundreds to thousands of hollow fiber membrane strands together and applied to a cooling tower (300). These modules are several to tens of meters 2 It has a specific surface area. Therefore, once the goal of moisture removal is determined, the number of modules can be designed accordingly, and there is scalability to connect them for use.

[0088] This membrane (100) can be recovered from a cooling tower (300) and, as shown in FIG. 2b, washed with water to remove the filler (120) from the hollow fiber membrane (110), and then regenerated by impregnating the filler (120) into the pores (112).

[0089] The foregoing description is merely an illustrative explanation of the technical concept of the present disclosure, and those skilled in the art to which the present disclosure pertains may make various modifications and variations within the scope of the essential characteristics of the technical concept. Furthermore, since these embodiments are intended to explain, not limit, the scope of the technical concept is not limited by these embodiments. The scope of protection of the present disclosure shall be interpreted by the claims below, and all technical concepts within an equivalent scope shall be interpreted as being included within the scope of rights of the present disclosure.

Claims

Claim 1 A pore-refilled hollow fiber membrane for water separation comprising a hollow fiber membrane having two or more pores, a first substance having a hydroxyl (-OH) group or a second substance having an amine (-NH2) group, a double crosslinking agent condensed with the first substance or the second substance, and a hydrophilic filler mixed with a viscous body and impregnated into each of the pores, wherein when a water drop is dropped on the surface of the hollow fiber membrane impregnated with the filler, the contact angle at which the water drop spreads is less than 10 degrees, and when the water drop is dropped on the surface of the hollow fiber membrane from which the filler has been removed, the contact angle at which the water drop spreads is 60 degrees or more. Claim 2 A pore-refilling hollow fiber membrane for water separation according to claim 1, wherein the first material is one of PVA (polyvinyl alcohol), PEG (polyethylene glycol), and cellulose, the second material is one of PEI (polyethyleneimine), gelatin, chitosan, and collagen, the double crosslinking agent is glutaraldehyde (GA), and the viscous material is glycerol or PEG (polyethylene glycol) with a molecular weight of 100 to 1000. Claim 3 delete Claim 4 A first step of newly manufacturing or reusing a hollow fiber membrane comprising two or more pores; a liquid viscous body comprising a first substance having a hydroxyl (-OH) group or an amine (-NH 2 A method for manufacturing a pore-refilled hollow fiber membrane for water separation, comprising: a second step of filling each of the pores with a mixture of a second substance having a ) group and a double crosslinking agent that crosslinks with the first substance or the second substance; and a third step of heat-treating the hollow fiber membrane to proceed with condensation polymerization of the first substance or the second substance and the double crosslinking agent to impregnate the pores of the hollow fiber membrane with a hydrophilic filler, wherein when a water drop is dropped on the surface of the hollow fiber membrane impregnated with the filler, the contact angle at which the water drop spreads is less than 10 degrees, and when the water drop is dropped on the surface of the hollow fiber membrane from which the filler has been removed, the contact angle at which the water drop spreads is 60 degrees or more. Claim 5 A method for manufacturing a pore-refilled hollow fiber membrane for water separation according to claim 4, wherein in the first step above, when the hollow fiber membrane is reused, the hollow fiber membrane from which the hydrophilic filler has been removed with water is reused. Claim 6 A method for manufacturing a pore-refilled hollow fiber membrane for water separation according to claim 4, wherein the first material is one of PVA (polyvinyl alcohol), PEG (polyethylene glycol), and cellulose, the second material is one of PEI (polyethyleneimine), gelatin, chitosan, and collagen, the double crosslinking agent is glutaraldehyde (GA), and the viscous material is glycerol or PEG (polyethylene glycol) with a molecular weight of 100 to 1000. Claim 7 delete Claim 8 An apparatus comprising a pore-refilled hollow fiber membrane for moisture separation according to claim 1 or 2. Claim 9 delete

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