KR20130011082A - Manufacturing method of multilayer metallic hollow fiber having porosity - Google Patents

Abstract

PURPOSE: A method of manufacturing a porous metal hollow fiber filter is provided to manufacture affordable and porous metal hollow fiber filter, has multi layers for continuously manufacturing precise filtration filter and reduce production costs due to simplified process and with no treatment process after coating process and ballast management for vessels is provided, too. CONSTITUTION: A method of manufacturing a porous metal hollow fiber filter comprises; a step to manufacture metal precursor solution by dispersing one type of metal powder chosen from transition metals, the oxide and alloys of the metal powder to a polymer solution, a step to manufacture a multi layered metal hollow fiber precursor by releasing the metal precursor solution through a multiple spinning nozzle(300), a step to manufacture a porous metal hollow fiber precursor by oxidizing the multi layered metal hollow fiber precursor and a step of sintering an oxidized porous metal hollow fiber filter.

Description

Manufacturing method of multilayer metallic hollow fiber having porosity

The present invention relates to a method for producing a multilayer metal hollow fiber filter medium having a porosity, and more particularly, to provide a method for manufacturing a multilayer metal hollow fiber filter medium capable of simultaneously forming multiple layers.

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, polymer hollow fiber membranes have a weak tensile strength and thus have a high risk of cutting, and in case of contamination of the membrane, it is difficult to recover permeate flow rate by a backwash method. 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 membrane is not high in temperature resistance and cannot be used for high temperature treatment materials. In the case of the reinforcement-reinforced hollow fiber membrane with no risk of cutting off, the polymer membrane coating layer is formed from the reinforcement material when backwashed by a backwash method. There was a problem that peeled off and could not use. In the case of improving the conventional problem, the ceramic separator may overcome some of the disadvantages of the polymer separator, but the use of the ceramic separator is extremely limited due to the problem of cracking during use.

Metal separators are produced in GKN, Germany, mainly in the form of tubes, but they are not spinning but are formed by pressing and molding metal particles on a certain frame and then sintering at high temperature and high pressure. Since the diameter of the tube is much larger than that of the hollow fiber membrane, the packing density per unit volume is very small. Therefore, it is used only in a special case in which it cannot be used as a polymer membrane due to its low competitiveness in the water treatment field. 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 separation membrane 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 single-walled metal hollow fiber described above, it is difficult to satisfy 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-described problem, the first problem to be solved of the present invention is to produce a multi-layered metal hollow fiber through the spinning method at the same time to form a multi-layer and high porosity multi-layer metal does not occur interlayer It is to provide a method for producing a hollow fiber filter medium.

The second problem to be solved of the present invention is to provide an apparatus for ship ballast water treatment employing the multilayer metal hollow fiber filter medium of the present invention.

In order to solve the above problems, 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 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 metal hollow fiber precursor having porosity; And (4) sintering the multilayer metal hollow fiber precursor in which the polymer is oxidized.

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 multi-nozzle of step (2) may be a double spinning nozzle or a triple spinning nozzle.

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 ℃.

According to another preferred embodiment of the present invention, the average particle diameter and the second particle diameter of the metal powder of the metal precursor solution is added to the first injection unit based on the center of the spinning nozzle when spinning the metal precursor solution to the triple spinning nozzle The average particle diameter of the metal powder of the metal precursor solution injected into the injection unit may be different.

According to another preferred embodiment of the present invention, when the metal precursor solution is radiated to the quadruple injection unit, the metal precursor solution introduced into the second injection unit based on the center is mixed with two or more kinds of metal powders having different average particle diameters. Can be added.

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 multilayer metal hollow fiber filter medium of the present invention.

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.

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

As described above, in the case of manufacturing the metal powder in the conventional molding die after compression and sintering, the production process is complicated, the production efficiency is lowered, and the relatively small particle size of powder in the process of forming a multilayer There is a problem that it is difficult to penetrate and control a multilayer having a desired pore size, porosity, and the like.

In addition, the conventional single-layer metal hollow fiber through the single-spinning nozzle not only has a limitation of high strength and average co-op, but also has a problem of additional process burden and reproducibility of coating when forming a multilayer again after forming a single layer by a spinning method. Furthermore, there is a problem that the metal powder of the newly formed outer layer penetrates into the pores of the monolayer already formed.

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 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 metal hollow fiber precursor having porosity; And (4) sintering the multilayer metal hollow fiber precursor in which the polymer is oxidized. Through this method, multiple layers can be formed at the same time while manufacturing the metal hollow fiber using the spinning method, so that high-strength and fine process control is possible, and the process can be simplified and the production cost can be reduced compared to the method of forming a multilayer after the formation of a single layer.

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.

Metal powders that can be used in the present invention can be used alone or in combination of transition metals, oxides thereof, and alloys that can be used for metal hollow fibers. Preferably the transition metal may be a 3 to 5 cycle transition metal, more preferably the transition metal may be any one of nickel, titanium, aluminum, copper, iron and stainless steel, most preferably produced It is more preferable to use nickel, which is very inexpensive, so that the manufacturing cost can be significantly lowered and the uniformity of the pore size can be secured.

In addition, the particle size of the metal powder is preferably maintained in the range of 0.005 ~ 20 ㎛ average particle diameter, if the particle size is less than 0.005 ㎛ the metal unit price is too high economical and 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 is a polymer that acts as a binder for forming the metal hollow fiber precursor after spinning is not particularly limited to those commonly used in the art, but is preferably oxidized (burned out) at a low temperature and then subjected to metal hollow fiber. It is preferable to use a polymer in which carbides are not formed. Preferably, the polymer may be oxidized at an oxidation temperature, more preferably, may be a synthetic polymer oxidized at 500 ° C. or less, and more preferably, polysulfone, polyamide, polyolefin, polyimide, Any one or more selected from the group consisting of cellulose acetate-based, polyvinyl-based, polystyrene-based, and polyether-based may be used, but is not limited thereto.

Also preferably, the polymer may include 5 to 50 parts by weight based on 100 parts by weight of the metal powder. If the amount of the added polymer is less than 5 parts by weight, the role of the binder is difficult to form a precursor, and if it exceeds 50 parts by weight, the viscosity of the solution is too large may cause a problem difficult to spin.

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 spinning nozzle used can be appropriately formed according to the size of the two-layered hollow fiber to be manufactured, and the thickness of the partition wall is also compared with the thickness of the partition wall of the conventional double spinning nozzle in order to improve the interlayer peeling force. It may be thinly formed, and may be 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 unit 305 is formed on the outer circumferential surface of the first injection unit 303 to form an outer layer of the two-layer hollow yarn, and an interlayer division is formed between the first injection unit 303 and the second injection unit 305. A second partition 304 is formed for this to emit a two-layer hollow fiber through it.

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 first injection unit 405 is formed on the outer circumferential surface of the third injection unit 403 to form a middle layer of the three-layer hollow yarn, and an interlayer division is formed between the third injection unit 403 and the first injection unit 405. The first partition 404 is formed. A second injection unit 407 is formed on the outer circumferential surface of the first injection unit 405 to form an outer layer of the three-layer hollow yarn, and an interlayer division is formed between the first injection unit 405 and the second injection unit 407. A second partition 406 may be formed.

According to a preferred embodiment of the present invention, the average particle diameter of the metal powder of the metal precursor solution to be injected into the first injection unit and the metal precursor solution to be injected into the second injection nozzle when the metal precursor solution is radiated to the double spinning nozzle The average particle diameter 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 final two-layered metal hollow yarn can be adjusted differently, which can significantly improve the filtration efficiency.

According to another preferred embodiment of the present invention, the metal precursor solution to be injected into the second injection unit based on the center when the metal precursor solution is radiated to the double spinning nozzles by mixing 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 unit may be added in two or more types, the first metal powder having an average particle diameter of 0.005 to 5 μm and the second having an average particle diameter of 3 to 20 μm. The metal powder may be mixed and added, and at the same time, the average particle diameter of the second metal powder may be 0.5 µm 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 the polymer means that the polymer is burned and removed by heating to a high temperature, through which pores are formed in the oxidized portion of the polymer.

The oxidation temperature is not limited as long as it can oxidize all the polymers, and 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 contracted by about 20%, thereby securing the required strength and the like 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. 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 multilayer metal hollow fiber filter medium manufactured by the above-described method does not generate 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.

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 multi-layered metal hollow fiber produced through the present invention can be widely used in water treatment 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 Preparation of Two-Layered Metal Hollow Fiber Using Triple Spinning Nozzle

A first metal precursor solution to form an inner layer was prepared. Specifically, 100 parts by weight of nickel powder having an average particle diameter of 5 µm 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. At this time, the diameter of the internal coagulating liquid injection unit is 0.7 mm, the diameter of the second injection unit (including the internal coagulating liquid injection unit) is 2.6 mm, and the diameter of the third injection unit (including the internal coagulating liquid injection unit and the first injection unit). Is 3.2 mm.

Thereafter, the spun metal hollow fiber precursor is solidified in distilled water. Thereafter, the precursor was immersed in water for one day to remove through exchange of solvent and water, and heated at 600 ° C. for 120 minutes to oxidize the polymer. Thereafter, the metal particles were sintered under a nitrogen / hydrogen atmosphere. Specifically, in the air atmosphere, after raising to 600 ℃ at 5 ℃ / min ascending rate and maintained for 2 hours to oxidize the polymer material and then maintained at 1200 ℃ for 2 hours at a rising rate of 5 ℃ / min to complete the sintering to 10 ℃ / min By cooling, a double metal hollow fiber filter medium was prepared.

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%. In addition, the thickness of the second metal filtration layer (outer layer) is 3 μm, the average size of pores is 1.1 μm, and the porosity is 32%. As a result of observing the cross section of the double metal hollow fiber filter medium, the interlayer penetration did not occur.

<Example 2>

Example 1 except for using a second metal precursor solution using 100 parts by weight of a metal powder obtained by mixing a first nickel powder having an average particle diameter of 5 μm and a second nickel powder having an average particle diameter of 2.5 μm at a weight ratio of 6: 1. In the same manner as the double metal hollow fiber filter medium was prepared.

Example 3 Preparation of Three-Layered Metal Hollow Fiber Using Quadruple Spinning Nozzle

8 parts by weight of polysulfone was added to 39 parts by weight of N-methyl-2-pyrrolidone with respect to 100 parts by weight of nickel powder having an average particle diameter of 10 µm in addition to the first metal precursor solution and the second metal precursor solution, which were the same as those of Example 1. This was stirred at 700 rpm to prepare a third metal precursor solution.

Water is supplied to the internal coagulation solution injection unit of the quadruple spinning nozzle disclosed in FIG. 7, a trimetal precursor solution is added to the third injection unit (inner layer), and the first metal is injected to the first injection unit (intermediate layer). The precursor solution was added and a second metal precursor solution was added to the second injection unit (outer layer).

At this time, the diameter of the internal coagulation liquid injection unit is 0.7 mm, the diameter of the first injection unit (including the internal coagulation liquid injection unit) is 2.6 mm, and the diameter of the second injection unit (including the internal coagulation liquid injection unit and the first injection unit). Is 3.2 mm. In addition, the diameter of the third injection portion (including the internal coagulation liquid injection portion and the first and second injection portions) is 3.7 mm.

Thereafter, the same procedure as in Example 1 was carried out to produce a three-layer metal hollow fiber filter medium.

The manufactured trimetal hollow fiber filter medium has a hollow of 0.8 μm, a first metal filtration layer (inner layer) having a thickness of 350 μm, an average size of pores of 4.5 μm, and a porosity of 40%. In addition, the thickness of the second metal filtration layer (intermediate layer) is 150 µm, the average size of the pores is 3.5 µm, and the porosity is 40%. In addition, the thickness of the third metal filtration layer (outer layer) is 3 μm, the average size of pores is 1.2 μm, and the porosity is 43%. As a result of observing the cross section of the triple metal hollow fiber filter medium, the interlayer penetration did not occur.

&Lt; Comparative Example 1 &

A first metal precursor solution was prepared to form a monolayer. Specifically, 100 parts by weight of nickel powder having an average particle diameter of 3 μm 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 metal precursor solution.

Thereafter, a single metal hollow fiber was prepared by spinning in a single spinning nozzle of FIG.

Comparative Example 2

N-methyl-2-pyrrolidone (NMP) was impregnated with a single metal hollow fiber prepared in Comparative Example 1 in a coating solution containing 5% by weight of nickel powder having an average particle diameter of 0.5 µm and polarized in an oven at 100 ° C. Volatilize the solvent. Then, the metal particles are sintered in a nitrogen / hydrogen atmosphere in a high temperature combustion furnace, and the flow rate of the mixed gas is 270 cc / min / unit, which is raised to 700 ° C. at 5 ° C./min ascending rate and maintained for 2 hours. Cool to 10 ° C./min.

As a result of observing the cross section of the coated metal hollow fiber, it was confirmed that the nickel powder contained in the coating liquid penetrated into the pores of the single layer hollow fiber.

Pore size (탆) Porosity (%) The tensile strength
(kgf / cm2) Water permeability
(LMH / bar) Example 1 1.1 32 75,000 12,300 Example 2 0.84 48 78,000 18,400 Example 3 1.2 43 84,000 17,500 Comparative Example 1 1.1 28 68,000 11,000 Comparative Example 2 0.64 23 71,000 6,800

As can be seen from Table 1, the multi-layered metal hollow fiber of Examples 1 to 3 radiated through the multi-radial nozzle of the present invention has a tensile strength and a water permeability compared to the single-layered metal hollow fiber radiated through the single radiation nozzle of Comparative Example 1. Markedly increased.

In addition, Comparative Example 2 in which the metal powder was coated on the single layer hollow fiber showed interlayer metal penetration, but this phenomenon did not occur in the multilayer metal hollow fibers of Examples 1 to 3 of the present invention. Furthermore, in the case of Comparative Example 2, the pore size was reduced, but the porosity and the tensile strength were reduced and the water permeability was significantly reduced compared to the example.

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

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

Claims (16)

(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 metal hollow fiber precursor having porosity; And
(4) sintering the multilayer metal hollow fiber precursor in which the polymer is oxidized. The method of claim 1,
The transition metal is a method for producing a multilayer metal hollow fiber filter medium having a porosity, characterized in that the three to five cycle transition metal. The method of claim 2,
The transition metal is nickel, titanium, aluminum, copper, iron and stainless steel, the method of producing a multilayer metal hollow fiber filter medium having a porous, characterized in that any one. The method of claim 1,
Method for producing a multilayer metal hollow fiber filter medium having a porosity, 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 multilayer 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 multi-layered 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 a method for producing a multilayer metal hollow fiber filter medium, characterized in that the polar solvent. The method of claim 7, wherein
The polar solvent is any one or more selected from the group consisting of N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide and dimethyl sulfoxide, 1-tridecanol and terpinol. Method for producing hollow fiber filter medium. The method of claim 1,
The metal precursor solution of step (1) is a method for producing a multilayer metal hollow fiber filter medium, characterized in that it comprises 5 to 50 parts by weight of polymer and 34 to 80 parts by weight of solvent with respect to 100 parts by weight of the metal powder. The method of claim 1,
The multi-spinning nozzle of the step (2) is a method of manufacturing a multi-layered metal hollow fiber filter medium, characterized in that the double spinning nozzle or triple spinning nozzle when the sealing portion for forming a hollow therein is provided. The method of claim 1,
The multi-spinning nozzle of step (2) is a multi-layered 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 multi-layer metal hollow fiber filter medium, characterized in that the polymer is oxidized at 300 ~ 700 ℃ in the step (3). The method of claim 1,
The sintering temperature of step (4) is a method for producing a multilayer metal hollow fiber filter medium, characterized in that 700 ~ 1400 ℃. The method of claim 11,
The average particle diameter of the metal powder of the metal precursor solution introduced into the first injection unit and the average particle diameter of the metal powder of the metal precursor solution introduced into the second injection unit differ from each other based on the center of the triple spinning nozzle. A method for producing a multilayer metal hollow fiber filter medium. The method of claim 11,
Multi-layered metal hollow fiber filter medium, characterized in that the metal precursor solution to be injected into the second injection unit based on the center when spinning the metal precursor solution to the triple spinning nozzle is mixed with two or more kinds of metal powders having a different average particle diameter Manufacturing method. 16. An apparatus for treating ballast water for a vessel comprising a multilayer metal hollow fiber filter medium produced by the method of any one of claims 1-15.

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