KR101348011B1 - Manufacturing method of metallic hollow fiber having porosity - Google Patents

Abstract

The present invention relates to a method for producing a metal hollow fiber filter medium having a porosity, and more particularly to a method for producing a water repellent layer on the surface of the metal hollow fiber filter medium produced by the spinning method to significantly improve the water repellency To provide.

Description

Manufacturing method of porous hollow fiber filter medium {Manufacturing method of metallic hollow fiber having porosity}

The present invention relates to a method for producing a metal hollow fiber filter medium having a porosity, and more particularly to a method for producing a water repellent layer on the surface of the metal hollow fiber filter medium produced by the spinning method to significantly improve the water repellency To provide.

Hollow fiber membrane is generally manufactured in the form of a thread having a central part like a macaroni. It is mainly used as a permeable membrane for removing fine impurities, and can be classified into a polymer hollow fiber membrane, a ceramic hollow fiber membrane, and a metal hollow fiber membrane. .

In general, the polymer hollow fiber metal hollow fiber filter medium has a weak tensile strength and thus a high risk of cutting, and it is difficult to recover the permeate flow rate by a backwashing method when contamination of the membrane occurs. In addition, there is a risk that the pores are collapsed by high backwash pressure, and in the case of chemical washing, there was a problem in changing the form and physical properties of the pores.

Furthermore, the polymer hollow fiber metal hollow fiber filter medium is not high in temperature resistance and cannot be used for high temperature treatment materials. In the case of the reinforcement type hollow fiber metal hollow fiber filter medium without the risk of cutting, when backwashed by a backwash method, There was a problem that the polymer metal hollow fiber filter medium coating layer peeled off from the reinforcing material and could not be used. In the case of the ceramic metal hollow fiber filter medium which has improved such a conventional problem, the disadvantages of the polymer metal hollow fiber filter medium can be overcome to some extent, but the use of the ceramic metal hollow fiber filter medium is very limited due to the problem of cracking during use.

Metal Metal hollow fiber filter media is produced in GKN, Germany, mainly in the form of a tube, but instead of spinning, the metal particles are squeezed to a certain frame and then sintered at high temperature and high pressure. It is a very high and high diameter hollow tube filter with a large diameter compared to the metal hollow fiber filter medium, so the packing density per unit volume is very small, which makes it difficult to use in water treatment. It is used. In addition, in the case of manufacturing by sintering after inserting the metal powder into the molding die, the production process is complicated, the production efficiency is reduced, and in the process of forming a multilayer, a relatively small particle size powder penetrates into the interior to reduce the porosity There was a problem.

In order to overcome the problems of the manufacturing process of the metal-metal hollow fiber filter medium by the powder sintering method, Korean Patent No. 10-0562043 discloses a manufacturing method of metal hollow fiber by the spinning method. The spinning method can reduce the production cost more than 30% compared to the powder sintering method described above, and can be widely used in the industrial field due to the high packing density per unit volume. By the way, the Korean Patent No. 10-0562043 describes only a method for manufacturing single layer hollow fiber using a single spinning nozzle. Specifically, Figure 1a is a cross-sectional view of a single spinning nozzle (1) used in the conventional spinning method, the single spinning nozzle is formed in the center of the seal 2 and the outer peripheral portion of the seal 2 and the spinning liquid is injected It is divided into a spinneret (3). The metal hollow fiber precursor may be prepared by injecting a spinning solution including a metal powder into the single spinning nozzle 1 and spinning the same. Figure 1b is another single spinning nozzle as an internal coagulating solution injection unit 5 for injecting an internal coagulating solution such as water to form a hollow in the center and the spinneret (6) ) Is formed.

However, in the case of the metal hollow yarn manufactured by the conventional spinning method described above, when raw water is exposed to alkali for a long time, the aging of the film is accelerated due to oxidation, and thus there is a problem in using cycles due to cutting and cracking.

Furthermore, in the case of the single-walled metal hollow fiber described above, there is a difficulty in satisfying both the strength, the transmittance, and the removal efficiency to be represented as a metal filter in a single layer. Therefore, in order to show high transmittance at uniform pore size, fine control is required in the sintering step, and is limited in average pore size and porosity. On the other hand, the multi-layered metal hollow yarn does not affect the separation from the inner layer to the support, and has the largest thickness in the multilayer. In the case of the outer layer, the average pore size and porosity are given for separation, which shows the advantage of easy control to the target pore size, and the thickness of the layer is thin, which lowers the resistance to pressure drop during permeation. Compared with construction, it shows an advantage in time in permeability and cleaning process. The multi-layered metal hollow yarn thus prepared can be variously controlled and applied by adjusting the metal particles while maintaining high strength and permeability in controlling the target pore size.

However, there is also a problem in the reproducibility of the additional process and coating in the case of forming a multilayer after manufacturing single-layer hollow fiber by the spinning method. In addition, there is a problem that the metal powder of the newly formed outer layer penetrates into the pores of the monolayer already formed.

The present invention has been made to solve the above problems, the first problem to be solved of the present invention is to provide a method for producing a metal hollow fiber filter medium that can maximize the water repellency while maintaining the porosity and pore size.

The second problem to be solved of the present invention is to provide a method for producing a multi-layered metal hollow fiber filter medium to form a plurality of layers at the same time while producing a hollow metal fiber through the spinning method and high porosity does not occur interlayer penetration.

It is a third object of the present invention to provide an apparatus for ballast water treatment and an air vent filter device employing the multilayer metal hollow fiber filter medium of the present invention.

In order to solve the first problem described above, the present invention comprises the steps of (1) preparing a metal precursor solution by dispersing any one or more metal powder and polymer selected from the group consisting of transition metals, oxides and alloys thereof in a solvent; (2) spinning the metal precursor solution through a spinning nozzle to produce a metal hollow fiber precursor; (3) treating the multilayer metal hollow fiber precursor at a high temperature to oxidize the polymer to produce a metal hollow fiber precursor having porosity; (4) sintering the metal hollow fiber precursor oxidized the polymer; And (5) forming a water-repellent layer on the surface of the metal hollow yarn.

According to a preferred embodiment of the present invention, the transition metal may be a 3 to 5 cycle transition metal.

According to another preferred embodiment of the present invention, the transition metal may be any one of nickel, titanium, aluminum, copper, iron and stainless steel.

According to another preferred embodiment of the present invention, the average particle diameter of the metal powder may be 0.005 ~ 20 ㎛.

According to another preferred embodiment of the present invention, the polymer may be a synthetic polymer that is oxidized at 500 ° C or less.

According to another preferred embodiment of the present invention, the polymer is selected from the group consisting of polysulfone-based, polyamide-based, polyolefin-based, polyimide-based, cellulose acetate-based, polyvinyl-based, polystyrene-based, and polyether-based It may be any one or more selected.

According to another preferred embodiment of the present invention, the solvent may be a polar solvent.

According to another preferred embodiment of the present invention, the polar solvent is N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide and dimethyl sulfoxide, 1- tridecanol and terpinol group It may be any one or more selected from.

According to another preferred embodiment of the present invention, the metal precursor solution of step (1) may include 5 to 50 parts by weight of polymer and 34 to 80 parts by weight of solvent based on 100 parts by weight of the metal powder.

According to another preferred embodiment of the present invention, the polymer may be oxidized at 300 to 700 ° C. in the step (3).

According to another preferred embodiment of the present invention, the sintering temperature of step (4) may be 700 ~ 1400 ℃.

Formation of the water repellent layer of step (5) can be achieved by coating on the surface of the porous metal hollow fiber filter medium.

According to another preferred embodiment of the present invention, the water repellent layer may be any one or more selected from the group consisting of a silane compound, a siloxane compound, a fluorine-based water repellent, Teflon, HMDS (hexamethyldisilazane) and silicon, more preferably Preferably, the silane compound may be trimethyl chlorosilane (TMSCL), amino silane (amino silane), alkyl silane (alkyl silane), and dimethyl dichlorosilane (DDS), and the siloxane compound may be polydimethyl siloxane (PDMS).

According to another preferred embodiment of the present invention, the thickness of the water repellent layer may be 0.01 ~ 50 ㎛.

In order to achieve the second object of the present invention, the spinning nozzle of step (2) may be a multi-spinning nozzle, more preferably a double spinning nozzle or a triple spinning nozzle.

According to another preferred embodiment of the present invention, the multi-spinning nozzle of step (2) may be a double spinning nozzle or a triple spinning nozzle when the sealing part for forming a hollow is provided therein.

According to another preferred embodiment of the present invention, the multi-spinning nozzle of step (2) may be a triple spinning nozzle or a quadruple spinning nozzle when the internal coagulating solution injection unit is provided to form a hollow therein. .

The pore size of the first layer of the multilayer metal hollow fiber filter medium may be 1-15 μm, the porosity is 30% or more, the pore size of the second layer is 0.1-10 μm, and the porosity may be 30% or more.

According to another preferred embodiment of the present invention, there is provided an apparatus for treating a ballast water vessel comprising the metal hollow fiber filter medium of the present invention.

Porous metal hollow fiber filter medium produced by the manufacturing method of the present invention has a slowing contact between the raw water and the metal support when applied to the treatment has the effect of preventing oxidation, when applied as an air vent filter, while maintaining the form under exothermic conditions water repellent Fine control of the thickness of the layer has the advantage that the moisture permeability is reduced.

Multi-layer metal hollow fiber according to the manufacturing method of the present invention is capable of producing an economical metal hollow fiber filter by using a spinning method, and it is possible to continuously manufacture a microfiltration filter having various pore sizes to give a multi-layer. In addition, since the post-treatment process such as coating is not performed to form the multilayer, the process can be simplified and the production cost can be reduced. In addition, since it is formed in multiple layers, the strength is improved compared to the single layer.

Furthermore, the multi-layered metal hollow fiber produced through the manufacturing method of the present invention does not generate the penetration of interlayer metals as compared with the conventional sintering method or the method of forming a multi-layer after single layer spinning. Controllable, the filtration efficiency is significantly improved.

1A and 1B are cross-sectional views of a single spinning nozzle used for spinning a conventional hollow metal fiber.
2 is a cross-sectional view of a dual spinning nozzle according to a preferred embodiment of the present invention.
3 is a cross-sectional view of a triple spinning nozzle according to a preferred embodiment of the present invention.
4 is a cross-sectional view of a triple spinning nozzle according to another preferred embodiment of the present invention.
5 is a cross-sectional view of a quadruple spinning nozzle according to another preferred embodiment of the present invention.
6 is a cross-sectional view of a single-layer metal hollow fiber filter medium having a water repellent layer formed thereon.
7 is a cross-sectional view of a two-layer metal hollow fiber filter medium having a water repellent layer formed thereon.
8 is a cross-sectional view of a three-layer metal hollow fiber filter medium having a water repellent layer formed thereon.

Hereinafter, with reference to the accompanying drawings the present invention will be described in more detail.

As described above, the metal hollow fiber filter medium manufactured by the conventional spinning method does not have a separate water-repellent layer, and when raw water is exposed to alkali for a long time, aging of the membrane is promoted due to oxidation, so that cutting or cracking occurs. The cycle becomes short, and in the case of the air vent filter using the polymer material, there is a problem that there is a risk of deformation when exposed to exothermic conditions for a long time.

Thus, the present invention comprises the steps of (1) preparing a metal precursor solution by dispersing any one or more metal powder and polymer selected from the group consisting of transition metals, oxides and alloys thereof in a solvent; (2) spinning the metal precursor solution through a spinning nozzle to produce a metal hollow fiber precursor; (3) treating the multilayer metal hollow fiber precursor at a high temperature to oxidize the polymer to produce a metal hollow fiber precursor having porosity; (4) sintering the metal hollow fiber precursor oxidized the polymer; And (5) forming a water-repellent layer on the surface of the metal hollow yarn. The porous metal hollow fiber filter medium manufactured through this process has a slowing contact between the raw water and the metal support when applied to the water treatment in which the water repellent layer is formed, and has an effect of preventing oxidation, and when applied as an air vent filter, the water repellent layer maintains its shape under heating conditions. By controlling the thickness of the finely has the effect of improving the moisture permeability.

First, as step (1), any one or more metal powders and polymers selected from the group consisting of transition metals, oxides and alloys thereof are dispersed in a solvent to prepare a metal precursor solution.

The metal powder which can be used in the present invention can be used alone or in combination of transition metals, oxides and alloys thereof which can be used in metal hollow fibers. Preferably, the transition metal may be a transition metal of three to five cycles, more preferably the transition metal may be any one of nickel, titanium, aluminum, copper, iron and stainless steel, It is more preferable to use nickel capable of remarkably lowering the cost of production and securing uniformity of pore size.

In addition, the particle size of the metal powder is preferably maintained in the average particle diameter range of 0.005 ~ 20 ㎛, if the particle size is less than 0.005 ㎛ the unit cost of the metal powder is too high economic efficiency and it is difficult to increase the content of the metal powder The strength of the final metal film is significantly reduced and there is a problem that sintering is not performed. When the thickness exceeds 20 μm, the pore size is formed to be 5 μm or more, so that the pore is too large to be used for water treatment. It is desirable to keep

The polymer used as a binder for forming a precursor in a metal after spinning is generally used in the art and is not particularly limited. Preferably, the polymer is oxidized (burned down) at a low temperature, It is preferable to use a polymer in which no carbide is formed. Preferably, the polymer may be a synthetic polymer that is oxidized at an oxidation temperature, more preferably at a temperature of 500 ° C or less, and more preferably a polysulfone type, a polyamide type, a polyolefin type, a polyimide type, Cellulose acetate type, polyvinyl type, polystyrene type, and polyether type may be used, but not limited thereto.

Preferably, the metal powder may include 5 to 50 parts by weight of the polymer based on 100 parts by weight of the metal powder. If the content of the added polymer is less than 5 parts by weight, it is difficult to form a precursor because the binder is difficult to form. If the amount of the polymer is more than 50 parts by weight, the viscosity of the solution becomes too large.

The solvent for dissolving the metal powder and the polymer is a polar solvent capable of dissolving the polymer, specifically N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide and dimethyl sulfoxide, 1- At least one selected from the group consisting of tridecanol and terpinol. The amount of the solvent may be appropriately used to the extent that the metal hollow fiber precursor can be prepared through spinning, and preferably, 34 to 80 parts by weight of the solvent may be used based on 100 parts by weight of the metal powder. If it is less than 34 parts by weight, it is difficult to uniformly dissolve the metal powder and polymer, and thus, it is difficult to prepare a metal hollow fiber precursor. If it exceeds 80 parts by weight, the spinning solution has a very weak viscosity, which makes it difficult to spin the nozzle. Can be lowered.

Next, as the step (2), the metal precursor solution is spun through a multispinning nozzle to prepare a multilayer metal hollow fiber precursor. The multi-spinning nozzle that can be used in the present invention is not particularly limited as long as it can produce a multi-layered metal hollow fiber, preferably, the multi-spinning nozzle is a double spinning nozzle or provided with a seal for forming a hollow inside It may be a triple spinning nozzle, it may be a triple spinning nozzle or a quadruple spinning nozzle when the internal coagulating solution injection unit is provided to form a hollow therein. On the other hand, the internal coagulation solution that can be used in the present invention can be used without limitation as long as it is conventionally used, preferably a polar solvent such as water and N-methyl-2-pyrrolidone, DMAc or an organic solvent such as ethanol, isopropanol May be used alone or in combination.

First, a multi-spinning nozzle having a closed portion formed therein for hollow formation will be described. FIG. 2 is a cross-sectional view of a double spinning nozzle 10 according to a preferred embodiment of the present invention. The first injection part 12 which forms the inner layer of the two-layer hollow fiber on the outer peripheral surface centering on (11), and the 2nd injection part 14 which forms the outer layer of the two-layer hollow yarn on the outer peripheral surface of the 1st injection part 12. Is provided, the partition wall 13 for the interlayer separation is formed between the first injection portion 12 and the second injection portion 14.

The size of the double-layered nozzles to be used can be appropriately formed in accordance with the size of the construction of the two-layered metal to be manufactured, and the thickness of the partition wall is also larger than the thickness of the partition wall of a conventional double- It may be formed to be thin, and preferably 0.5 to 3 mm.

Figure 3 is a cross-sectional view of a triple spinning nozzle formed with a seal according to a preferred embodiment of the present invention. The first injection part 22 which forms the 1st layer of a three-layer hollow fiber on the outer peripheral surface centering on the sealing part 21 which forms the hollow part of hollow fiber inside, and the 2nd layer on the outer peripheral surface of the 1st injection part 22 The second injection unit 24 is formed to form a first partition wall between the first injection unit 22 and the second injection unit 24 is formed. In addition, a third injection unit 26 is formed on the outer circumferential surface of the second injection unit 24 to form an interlayer between the second injection unit 24 and the third injection unit 26. The second partition 25 is formed.

Next, referring to the multi-spinning nozzle formed therein the internal coagulating liquid injection portion for forming the hollow, Figure 4 is a cross-sectional view of a triple spinning nozzle 300 according to a preferred embodiment of the present invention, the hollow hollow inside A first injection unit 303 is formed on the outer circumferential surface of the inner coagulating liquid injection unit 301 to form an inner layer of the hollow fiber, and is formed between the internal coagulating liquid injection unit 301 and the first injection unit 303. The first partition 302 may be provided. A second injection part 305 for forming an outer layer of a two-layer hollow fiber is provided on the outer circumferential surface of the first injection part 303 and an interlayer separation is formed between the first injection part 303 and the second injection part 305 A second barrier rib 304 is formed for radiating a two-layer metal construction.

The size of the triple spinning nozzle to be used can be appropriately formed according to the size of the two-layer metal hollow fiber to be manufactured, and the thickness of the first and second partition walls is also a conventional double spinning nozzle to improve the interlayer peeling force. It may be thinner than the thickness of the partition wall, and may be preferably 0.5 to 3mm.

FIG. 5 is a cross-sectional view of the quadruple spinning nozzle 400. A third injection unit 403 forming an inner layer of a three-layer hollow yarn on an outer circumferential surface of an inner coagulating liquid injection unit 401 forming a hollow yarn therein is provided. The third partition 402 may be provided between the internal coagulating solution injection part 401 and the third injection part 403. A third injection unit 403 is provided with a first injection unit 405 forming an intermediate layer of a three-layer hollow fiber on the outer circumferential surface of the third injection unit 403 and an interlayer distinction is formed between the third injection unit 403 and the first injection unit 405 A first barrier rib 404 is formed. A second injection part 407 for forming an outer layer of a three-layer hollow fiber is provided on the outer circumferential surface of the first injection part 405 and an interlayer separation is formed between the first injection part 405 and the second injection part 407 A second barrier rib 406 may be formed.

According to a preferred embodiment of the present invention, when the metal precursor solution is radiated to the dual spinneret, the average particle diameter of the metal powder of the metal precursor solution injected into the first injection part and the average particle diameter of the metal precursor solution The average particle size of the metal powder may be different. In this case, the size and porosity of the pores of the outer layer and the inner layer of the finally produced two-layer metal hollow fiber can be controlled differently, and the filtration efficiency can be remarkably improved.

According to another preferred embodiment of the present invention, when the metal precursor solution is radiated to the double spinning nozzle, the metal precursor solution to be injected into the second injection portion with respect to the center is mixed with two or more kinds of metal powders having different average particle diameters Can be added.

Preferably, the average particle diameter of the metal powder to be injected into the second injection part can be divided into two or more kinds. The first metal powder having an average particle diameter of 0.005 to 5 μm and the second metal powder having an average particle diameter of 3 to 20 μm And the average particle diameter of the second metal powder may be 0.5 mu m or more larger than the average particle diameter of the first metal powder.

The coagulation bath for coagulating the polymer solution after spinning may use alcohol, water, and a specific solvent, but it is preferable to consider water in terms of economics. In this case, if the temperature of the coagulation bath is lower than 0 ° C., the precursor after spinning is rapidly reduced. It may be coagulated and cause a slight crack in the precursor. If it exceeds 70 ° C, the solvent vaporizes and is harmful to the body. Therefore, the temperature of the water-based coagulation bath is preferably maintained in the range of 0 to 70 ° C.

Next, in step (3), the multilayer metal hollow fiber precursor is treated at high temperature to oxidize the polymer to prepare a multilayer metal hollow fiber precursor having porosity. Oxidation of a polymer means heating to a high temperature to burn off the polymer, which results in the formation of pores in the oxidized portion of the polymer.

The oxidation temperature is not particularly limited as long as the polymer can be oxidized at all, preferably, the polymer can be oxidized at 300 to 700 ° C and the oxidation time can be performed for 0.5 to 3 hours, but is not limited thereto.

Next, as a step (4), the multilayer metal hollow fiber precursor in which the polymer is oxidized is sintered. Through the sintering process, the multilayer metal hollow fiber precursor is shrunk by about 20%, thereby securing the necessary strength and reducing the pore size.

Preferably, the sintering temperature of the step (4) may be 700 ~ 1400 ℃, the gas atmosphere may be used alone or in a mixture of nitrogen, argon, hydrogen and the like as a conventional atmosphere. The sintering time may be 1-4 hours.

When the multilayer metal hollow fiber filter medium manufactured according to the present invention has two layers, the pore size of the inner layer may be 1-15 μm, the porosity may be 30-70%, and the pore size of the outer layer is 0.1-10 μm, and the porosity is May be 30-50%.

In the case of three layers, the pore size of the inner layer may be 1-15 μm and the porosity may be 30-70%. The pore size of the middle layer may be 1-10 μm and the porosity may be 30-70%. The size may be 0.1-10 μm and the porosity may be 30-50%.

The multi-layered metal hollow fiber filter manufactured through the above-described method does not cause interlayer penetration. That is, the metal powder forming the first metal filtration layer does not penetrate into the second metal filtration layer or the metal powder forming the second metal filtration layer does not penetrate into the first metal filtration layer. In addition, even when the third metal filtration layer is formed, interlayer penetration does not occur in the same manner.

Next, as a step (5) to form a water repellent layer on the surface of the metal hollow fiber filter medium. The method of water-repellent surface treatment on the surface of the metal hollow yarn is not particularly limited, and may be performed by a variety of known surface treatment methods, the surface treatment method is well known in the art, so the detailed description thereof Omit.

6 is a cross-sectional view of a single-layer metal hollow fiber filter medium having a water repellent layer, and includes a hollow 300, a metal filtration layer 301 surrounding the hollow, and a water repellent layer 302 formed on the surface of the metal filtration layer 301. .

7 is a cross-sectional view of a two-layer metal hollow fiber filter medium having a water repellent layer formed therein, the hollow 310, the first metal filtration layer 311 surrounding the hollow, and the second metal filtration layer surrounding the first metal filtration layer 311. 312 and a water repellent layer 313 formed on the surface of the second metal filtration layer 312.

8 is a cross-sectional view of a three-layer metal hollow fiber filter medium having a water repellent layer, the hollow 320, the first metal filtration layer 321 surrounding the hollow, and the second metal filtration layer surrounding the first metal filtration layer 321. 322, a third metal hollow fiber filtration layer 323 surrounding the second metal hollow fiber filtration layer 322, and a water repellent layer 324 formed on a surface of the third metal filtration layer 323.

In one preferred embodiment, the water repellent surface treatment can be achieved through a method of coating a water repellent material on the surface of the metal hollow yarn. The method of adding the water-repellent material to the surface of the metal hollow fiber filter medium is not particularly limited, and may be a flow coating method, a spin coating method, a dip coating method, a bar coating method, or a bar coating method. It may be formed by a variety of methods, such as). As a specific example, the metal hollow fiber filter medium may be immersed in a solution in which the water repellent material is dispersed, or a dispersion of the water repellent substance may be performed on the surface of the metal hollow fiber filter medium by the spray coating method. It is also possible to vaporize the water repellent material and deposit it on the surface of the metal hollow fiber filter medium. In order to increase the binding force of the water-repellent material to the surface of the metal hollow fiber filter medium in the coating process, a predetermined binding aid may be added. For example, a fluorine-based compound such as PVdF, PTFE, etc. may be added to a solvent such as NMP and a clay mineral. Coating may be performed by applying a coating solution containing a polymer, a PVdF-based copolymer polymer, PMMA, PAN, PEO, SBR, and the like to a metal hollow fiber filter medium.

The water-repellent material is a material with low chemical reactivity, and may be various without particular limitation as long as it is surface treated to the metal hollow fiber filter medium to impart water repellency, for example, water repellent organic particles, water repellent inorganic particles, water repellent surface coating inorganic particles And it may be one or two or more selected from the group consisting of water-repellent surface coating organic particles.

Examples of the water-repellent surface-coated organic particles and the water-repellent surface-coated inorganic particles include hydrophilic organic or inorganic particles having water repellency added to the surface by coating with a water-repellent organic material. Especially, the water-repellent silane compound and / or siloxane compound which consist of substituents with low chemical reactivity are preferable.

In one preferred embodiment, the water repellent material may be any one or more selected from the group consisting of the silane-based compound, siloxane-based compound, fluorine-based water repellent, Teflon, hexamethyldisilazane (HMDS) and silicon, more preferably The silane compound may be trimethyl chlorosilane (TMSCL), amino silane (alkyl silane), alkyl silane (alkyl silane), and dimethyl dichlorosilane (DDS), and the siloxane compound may be polydimethyl siloxane (PDMS).

On the other hand, according to another preferred embodiment of the present invention, the thickness of the water repellent layer may be 0.01 ~ 50 ㎛.

The porous metal hollow fiber filter medium produced by the manufacturing method of the present invention has an effect of preventing oxidation by slowing the contact between raw water and the metal support when applied to water treatment, and maintaining water-repellent shape while maintaining the form under exothermic conditions when applied as an air vent filter. By controlling the thickness of the layer finely, the moisture permeability is improved.

The multi-layered metal hollow fiber produced through the present invention can be widely used in water treatment filters, microfiltration filters, vessel ballast water treatment apparatus and the like.

The following examples illustrate the invention in more detail. The following examples are presented to help the understanding of the present invention, but the present invention is not limited thereto.

≪ Example 1 >

A first metal precursor solution to form an inner layer was prepared. Specifically, 100 parts by weight of a nickel powder having an average particle diameter of 5 탆 and 8.6 parts by weight of polysulfone were added to 34.3 parts by weight of N-methyl-2-pyrrolidone and stirred at 700 rpm to prepare a first metal precursor solution.

A second metal precursor solution was formed to form the outer layer. Specifically, 100 parts by weight of nickel powder having an average particle diameter of 2.5 μm. 10 parts by weight of polysulfone was added to 42 parts by weight of N-methyl-2-pyrrolidone and stirred at 700 rpm to prepare a second metal precursor solution.

Water was supplied to the internal coagulation solution injection unit of the triple spinning nozzle disclosed in FIG. 4, a first metal precursor solution was added to the first injection unit, and a second metal precursor solution was added to the second injection unit. In this case, the diameter of the inner coagulating solution injection part is 0.7 mm, the diameter of the second injection part (including the inner coagulating solution injection part) is 2.6 mm, the diameter of the third injection part (including the inner coagulating solution injection part and the first injection part) Is 3.2 mm.

The spun metal hollow fiber precursor is then coagulated in distilled water. Subsequently, the precursor was immersed in water for one day, removed through exchange of solvent and water, and heated at 600 ° C for 120 minutes to oxidize the polymer. Thereafter, the metal particles were sintered in a nitrogen / hydrogen atmosphere. Specifically, the polymer material was oxidized by raising the temperature to 600 ° C at an increasing rate of 5 ° C / min in an air atmosphere, and the polymer material was oxidized at a rising rate of 5 ° C / min for 2 hours at a rising rate of 10 ° C / min Followed by cooling to prepare a double metal hollow fiber filter medium.

The manufactured double metal hollow fiber filter medium had a hollow of 0.8 mm, a thickness of the first metal filtration layer (inner layer) of 400 μm, an average size of pores of 3.5 μm, and a porosity of 40%. Further, the thickness of the second metal filtration layer (outer layer) is 3 占 퐉, the average size of the pores is 1.1 占 퐉, and the porosity is 32%. As a result of observing the cross section of the double metal hollow fiber filter medium, no intercalation phenomenon occurred.

Thereafter, the prepared double metal hollow fiber filter medium was surface-treated in a silicone oil dip coating method to prepare a water repellent layer.

<Example 2>

Except for coating the Teflon instead of silicone oil was carried out in the same manner as in Example 1 to prepare a metal hollow fiber filter medium having a water repellent layer.

<Comparative Example>

A metal hollow fiber filter medium was prepared in the same manner as in Example 1 except that the water repellent layer was not formed.

Experimental Example

The following evaluations were performed on the metal hollow fiber filter media prepared in Examples 1, 2 and Comparative Examples, and the results are shown in Table 1.

1. Pure transmittance measurement

In order to evaluate the permeability of the metal hollow fiber filter medium, the pure water at room temperature was pressurized under a constant pressure (1 bar), and the amount of filtered water was measured for a certain time by an outside-in method, and then the unit membrane area and the unit time were measured. Converted to.

2. Measurement of moisture permeability

In order to evaluate the moisture permeability of the metal hollow fiber filter medium, hollow fiber was module-modified with epoxy, the silica gel was quantitatively dried inside, sealed, and then exposed to the outside for 24 hours to check the color change of the silica gel. At this time, the silica gel turns colorless when it is saturated from blue when dried.

division coating Macroscopic coating layer
Thickness (um) Pore size (um) Pitcher
(L / m ² h) Moisture permeability color change Example 1 Silicon 0.8 0.98 11,160 Blue Example 2 PTFE 1.5 0.82 10,200 Blue Comparative Example X X 1.1 12,300 Colorless

As can be seen from Table 1, in Examples 1 to 2 including the water repellent layer of the present invention, it can be seen that the permeation of moisture was remarkably removed as compared with the comparative example without the water repellent layer.

In addition, the pore size and permeability resulted in the reduction of porosity and permeability, but it can be seen that the water repellent layer acts as a separation layer of the filter, so that the pore size and permeability vary depending on the characteristics of the water repellent layer.

The multi-layered metal hollow fiber produced through the present invention can be widely used for water treatment filters, ship ballast water treatment devices, and air vent filter devices.

10: double spinning nozzle 11: sealing part
12: first injection portion 13: partition wall
14: second injection unit

Claims (19)

(1) preparing a metal precursor solution by dispersing any one or more metal powders and polymers selected from the group consisting of transition metals, oxides and alloys thereof in a solvent;
(2) spinning the metal precursor solution through a multi-spinning nozzle to produce a multilayer metal hollow fiber precursor;
(3) treating the multilayer metal hollow fiber precursor at a high temperature to oxidize the polymer to produce a multilayer porous metal hollow fiber precursor having porosity;
(4) preparing a multilayer porous metal hollow fiber by sintering the multilayer porous metal hollow fiber precursor in which the polymer is oxidized; And
(5) forming a water repellent layer on the surface of the multilayer porous metal hollow yarn,
The metal precursor solution of step (1) comprises 5 to 50 parts by weight of polymer and 34 to 80 parts by weight of solvent based on 100 parts by weight of the metal powder,
The multilayer porous metal hollow yarn includes an inner layer and an outer layer,
The thickness of the water repellent layer is 0.1 ~ 50 ㎛,
Method for producing a porous metal hollow fiber filter medium, characterized in that the average pore size of the outer layer is 0.1 ~ 1 ㎛.
The method of claim 1,
The transition metal is a method for producing a porous metal hollow fiber filter medium, characterized in that 3 to 5 cycle metal transition. 3. The method of claim 2,
The transition metal is a method for producing a porous metal hollow fiber filter medium, characterized in that any one of nickel, titanium, aluminum, copper, iron and stainless steel. The method of claim 1,
Method for producing a porous metal hollow fiber filter medium, characterized in that the average particle diameter of the metal powder is 0.005 ~ 20 ㎛. The method of claim 1,
The polymer is a method for producing a porous metal hollow fiber filter medium, characterized in that the synthetic polymer is oxidized at 500 ℃ or less. The method of claim 5,
The polymer is a porous metal hollow, characterized in that at least one selected from the group consisting of polysulfone, polyamide, polyolefin, polyimide, cellulose acetate, polyvinyl, polystyrene, and polyether. Method for producing four filter media. The method of claim 1,
The solvent is at least one selected from the group consisting of N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide and dimethyl sulfoxide, 1-tridecanol and terpinol. Method for producing four filter media.
delete delete The method of claim 1,
The multi-spinning nozzle of the step (2) is a method of manufacturing a porous metal hollow fiber filter medium, characterized in that the double spinning nozzle or triple spinning nozzle when the sealing part for forming a hollow is provided therein. The method of claim 1,
The multi-spinning nozzle of the step (2) is a method of manufacturing a porous metal hollow fiber filter medium, characterized in that the triple spinning nozzle or quadruple spinning nozzle when the internal coagulating solution injection unit is provided to form a hollow therein. The method of claim 1,
Method for producing a porous metal hollow fiber filter medium, characterized in that the oxidizing the polymer at 300 ~ 700 ℃ in the step (3). The method of claim 1,
The sintering temperature of step (4) is a method for producing a porous metal hollow fiber filter medium, characterized in that 700 ~ 1400 ℃. The method of claim 1,
Formation of the water-repellent layer of step (5) is a method of producing a porous metal hollow fiber filter medium, characterized in that is achieved by coating on the surface of the porous metal hollow fiber filter medium. The method of claim 1,
The water-repellent layer is a method for producing a porous metal hollow fiber filter medium, characterized in that any one or more selected from the group consisting of a silane compound, a siloxane compound, a fluorine-based water repellent, Teflon, HMDS (hexamethyldisilazane) and silicon. 16. The method of claim 15,
The silane compound is TMSCL (trimethyl chlorosilane), amino silane (amino silane), alkyl silane (alkyl silane) and DDS (dimethyl dichlorosilane), the siloxane compound is a porous metal hollow fiber, characterized in that the PDMS (polydimethyl siloxane) Method for producing filter medium. delete An apparatus for treating ballast water for a vessel comprising a porous metal hollow fiber filter medium prepared by the method of any one of claims 1 to 7 and 10 to 16.
An air vent filter device comprising a porous metal hollow fiber filter medium prepared by the method of any one of claims 1 to 7 and 10 to 16.

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