KR101328751B1 - Manufacturing method of metallic hollow fiber preventing bending - Google Patents

Abstract

The present invention relates to a method for producing a metal hollow fiber filter medium that can solve the warpage and cut-off of the metal hollow fiber precursor generated after the winding in the bobbin during the production of the metal hollow fiber filter medium by the spinning method.

Description

Manufacturing method of metallic hollow fiber preventing bending

The present invention relates to a method of manufacturing a metal hollow fiber filter medium to prevent bending, and more particularly, when the metal hollow fiber filter medium is produced by the spinning method, the surface of the metal hollow yarn becomes very rough or the metal is generated after winding or free spinning on a bobbin. It is to provide a method for manufacturing a metal hollow fiber filter medium that can solve the warpage phenomenon and the cutting out of the hollow fiber precursor.

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 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. Specifically, the spinning method coagulates a metal precursor solution through free spinning through a spinning nozzle, and then deposits it in water for one day to prepare a precursor or to wind it into a bobbin. However, when the metal hollow fiber is manufactured by the conventional spinning method, not only the surface of the metal hollow yarn is excessively roughened through a coagulation process or a bobbin winding process, but there is a problem that the metal hollow fiber precursor is bent in these processes.

Specifically, Figure 1 is a photograph of a conventional metal hollow fiber precursor collection process by free spinning. When the precursor is prepared using a conventional spinning method, not only the process problem of forcibly imparting the straightness of the precursor in the process of unwinding the metal hollow fiber precursor prepared, but also inherent in the possibility of cutting. In addition, there is a problem that the deflection phenomenon is provided by providing a shrinking direction and the surface of the precursor is not smooth.

FIG. 2 is a photograph of a metal hollow fiber precursor fabricated using a metal hollow fiber precursor prepared by free spinning, which is a warpage phenomenon.

On the other hand, in the conventional spinning using a metal hollow fiber precursor, hollow fiber is collected by winding using a bobbin. 3 is a perspective view of a winding unit in which a metal hollow yarn is wound in a conventional bobbin, and FIG. 4 is a cross-sectional view of the winding unit. However, when the solution containing the metal particles are wound in the bobbin as described above, the surface of the emitted precursor is not smooth or cut off, which makes it difficult to apply. In addition, there was a problem that the bending phenomenon occurs.

The present invention has been made to solve the above problems, the first problem to be solved of the present invention is to produce a metal hollow fiber filter medium by the conventional spinning method, the surface of the metal hollow yarn becomes very rough or occurs after winding or free spinning on the bobbin It is to provide a method for uniformly manufacturing the metal hollow fiber filter medium without bending and cutting of the metal hollow fiber precursor.

The second problem to be solved of the present invention is to provide an apparatus for treating water ballast (ballast) using the metal hollow fiber filter medium of the present invention.

The second problem to be solved of the present invention is to provide an apparatus for treating water ballast (ballast) using the 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, polymer binder selected from the group consisting of transition metals, oxides and alloys thereof in a solvent; (2) while simultaneously spinning the metal precursor solution and the polymer coating solution using the multi-radiation nozzle, injecting the polymer coating solution into the outermost injection portion of the multi-radiation nozzle so that the polymer coating solution can be coated on the surface of the metal hollow fiber precursor after spinning Preparing a metal hollow fiber precursor coated with a polymer; (3) treating the polymer-coated metal hollow fiber precursor at a high temperature to oxidize the polymer binder and the coated polymer to produce a metal hollow fiber precursor having porosity; And (4) sintering the metal hollow fiber precursor in which the polymer binder and the coated polymer are oxidized.

According to a preferred embodiment of the present invention, the polymer binder may be a synthetic polymer oxidized at the oxidation temperature.

According to another preferred embodiment of the present invention, the polymer binder 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 polymer of the polymer coating liquid may be a material that can be thermally decomposed at the oxidation temperature of step (3) and below.

According to another preferred embodiment of the present invention, the polymer of the polymer coating liquid may be a material that can be thermally decomposed at 500 ℃ or less.

According to another preferred embodiment of the present invention, the polymer of the polymer coating solution is polysulfone, polyamide, polyolefin, polyimide, cellulose acetate, polyvinyl, polystyrene, polyether and thermoplastic The elastomer may be any one or more selected from the group consisting of elastomers, in which case the thermoplastic elastomer may be a nylon elastomer, a silicone elastomer, a polyolefin elastomer, a PET elastomer, a polyurethane elastomer, or a PVC elastomer.

According to another preferred embodiment of the present invention, it may further comprise winding and unwinding the metal hollow fiber precursor coated with the polymer in the bobbin between the step (2) and (3).

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

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 central spinning nozzle may be a triple spinning nozzle, a quadruple spinning nozzle or a five spinning nozzle when the internal coagulating fluid injection unit is provided to form a hollow therein. In the case where the sealing part for forming a hollow is provided, the nozzle may be a double spinning nozzle, a triple spinning nozzle or a quadruple spinning nozzle.

According to another preferred embodiment of the present invention, the thickness of the polymer coating layer of the step (2) may be 0.1 ~ 500 ㎛.

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

The metal hollow fiber produced by the method of the present invention is a method of spinning the metal hollow fiber precursor through a multi-radiation nozzle during the production of the metal hollow fiber filter medium by the spinning method and at the same time the polymer is coated on the surface of the precursor, so that the coated polymer is solidified after the process In the effect of supporting the surface of the precursor is not rough.

In addition, it is possible to minimize the mass production of defective products can be solved after the free spinning without winding on the bobbin or the bending phenomenon and cutting of the hollow metal fiber generated after winding and unwinding on the bobbin.

1 is a photograph of a precursor collection process by a conventional free spinning.
2 is a photograph of a metal hollow fiber manufactured using a metal hollow fiber precursor prepared through free spinning.
3 is a perspective view of a winding part included in a bobbin used in manufacturing a conventional hollow metal fiber, and FIG. 4 is a cross-sectional view of the winding part.
5 is a cross-sectional view of a dual spinning nozzle according to a preferred embodiment of the present invention.
6 is a cross-sectional view of a triple spinning nozzle according to a preferred embodiment of the present invention.
7 is a cross-sectional view of a triple spinning nozzle according to another preferred embodiment of the present invention.
8 is a cross-sectional view of a quadruple spinning nozzle according to another preferred embodiment of the present invention.

Hereinafter, the present invention will be described in more detail.

As described above, in the conventional spinning method, the metal precursor solution is solidified through free spinning through a spinning nozzle and then deposited in water for one day to prepare a precursor or to wind it into a bobbin. However, when the metal hollow fiber is manufactured by the conventional spinning method, not only the surface of the metal hollow yarn is excessively roughened through a solidification process or a bobbin winding process, but also a metal hollow fiber precursor is bent or cut in these processes.

Thus, the present invention comprises the steps of (1) preparing a metal precursor solution by dispersing any one or more metal powder, polymer binder selected from the group consisting of transition metals, oxides and alloys thereof in a solvent; (2) while simultaneously spinning the metal precursor solution and the polymer coating solution using the multi-radiation nozzle, injecting the polymer coating solution into the outermost injection portion of the multi-radiation nozzle so that the polymer coating solution can be coated on the surface of the metal hollow fiber precursor after spinning Preparing a metal hollow fiber precursor coated with a polymer; (3) treating the polymer-coated metal hollow fiber precursor at a high temperature to oxidize the polymer binder and the coated polymer to produce a metal hollow fiber precursor having porosity; And (4) sintering the metal hollow fiber precursor in which the polymer binder and the coated polymer are oxidized. When the metal hollow fiber filter medium is produced by the spinning method, the metal hollow fiber precursor is produced through the multi-radiation nozzle and the polymer is coated on the surface of the precursor, so that the coated polymer is not coarsened in a subsequent process such as solidification. Has the effect of In addition, it is possible to minimize the mass production of defective products can be solved after the free spinning without winding on the bobbin or the bending phenomenon and cutting of the hollow metal fiber generated after winding and unwinding on the bobbin.

First, as step (1), any one or more metal powders and polymer binders 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 maintain.

next. The polymer binder plays a role of a binder for forming a metal hollow fiber precursor after spinning and forms a pore by being oxidized in an oxidation process, and the polymer is generally used in the art, but is not particularly limited, but is preferably low. It is preferable to use a polymer that is oxidized (burned and extinguished) at a temperature and then no carbide is formed in the metal hollow fiber. Preferably, the polymer binder may be one that can be oxidized at the oxidation temperature of step (3), and more preferably may be a synthetic polymer that is oxidized at 500 ° C. or less. Specifically, any one or more selected from the group consisting of polysulfone, polyamide, polyolefin, polyimide, cellulose acetate, polyvinyl, polystyrene, and polyether may be used, but is not limited thereto. .

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

The solvent for dissolving the metal powder and the polymer binder 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 produced by 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 binder, and thus, it is difficult to prepare a metal hollow fiber precursor. If it exceeds 80 parts by weight, the viscosity of the spinning solution is very weak, making nozzle spinning difficult and the strength of the manufactured metal hollow fiber. Can be lowered.

Next, (2) while simultaneously spinning the metal precursor solution and the polymer coating solution using the multi-radiation nozzle, the polymer coating solution to the outermost injection portion of the multi-radiation nozzle so that the polymer coating solution can be coated on the surface of the metal hollow fiber precursor after spinning Injecting to prepare a metal hollow fiber precursor coated with a polymer.

In the case of manufacturing the metal hollow fiber by the conventional spinning method, not only the surface of the metal hollow yarn is excessively roughened through a solidification process or a bobbin winding process, but also there is a problem that the metal hollow fiber precursor is bent or cut in these processes. In particular, when the bending phenomenon occurs, there was a problem that the hardened state is not restored again.

Accordingly, in the present invention, the polymer coating solution was simultaneously spun using a multispinning nozzle when spinning the metal precursor solution. Since the polymer is coated on the surface of the metal hollow fiber precursor in the spinning process it can solve the problem that the surface of the metal hollow fiber precursor is too rough through the coagulation process or bobbin winding process.

Furthermore, it is possible to minimize the mass production of defective products by free spinning without winding on the bobbin or the bending phenomenon and cutting of the hollow metal fiber generated after winding and unwinding on the bobbin can be solved. When the polymer-coated hollow fiber precursor coated on the bobbin and then unwound it is restored to the original state in the bent state by the elastic force of the coated polymer. After heating to a high temperature in the oxidation process, all of the coated polymers are thermally decomposed, and thus the final polymer produced through the sintering process does not include the coated polymer.

After all, the polymer coating of the present invention utilizes the physical properties of elasticity and surface protection, not the chemical properties related to the molecular formula of the polymer, and the coated polymer can be thermally decomposed with restoring force since all of the coated polymers are thermally decomposed in a subsequent process. If it is a polymer can be used without limitation.

Meanwhile, preferably, the polymer of the polymer coating liquid may be a material that can be thermally decomposed at an oxidation temperature or less, and more preferably, the coated polymer may be a material that can be pyrolyzed at 500 ° C. or less.

According to another preferred embodiment of the present invention, the coated polymer is polysulfone-based, polyamide-based, polyolefin-based, polyimide-based, cellulose acetate-based, polyvinyl-based, polystyrene-based, polyether-based and thermoplastic elastomer It may be any one or more selected from the group consisting of, in this case, the thermoplastic elastomer may be a nylon elastomer, a silicone elastomer, a polyolefin elastomer, a PET elastomer, a polyurethane elastomer, a PVC elastomer, but is not limited thereto It can be used to impart restoring force to the metal hollow fiber precursor, and may be used without limitation as long as it can be oxidized with the polymer. Thermoplastic elastomers (TPE) mean elastomers that can be molded at high temperature as thermoplastics and exhibit rubber elastomer properties at room temperature.

The solvent of the polymer coating solution may be used a solvent that is commonly used, preferably N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide and dimethyl sulfoxide, 1- tridecanol and terpinol Can be used but is not limited thereto. The concentration of the polymer coating solution may also be the concentration of a conventional coating solution, preferably 5 to 30% by weight of the polymer, but is not limited thereto.

On the other hand, the thickness of the coating layer is not particularly limited, but may be preferably 0.1 ~ 500㎛.

On the other hand, the present invention is to coat the polymer on the surface of the metal hollow fiber precursor during the spinning process using a multi-spinning nozzle, in this case can be used in the present invention The multi-spinning nozzle is preferably an internal coagulation solution for the hollow formation Single-layer metal hollow fiber may be manufactured by using a spinning nozzle including an injection unit or a spinning nozzle including a sealed part (hollow formation) therein. In this case, if the internal coagulating solution injected through the internal coagulating solution injection unit is capable of forming a hollow in the metal hollow fiber precursor, a conventional internal coagulating solution may be used. 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, dimethyl acetylamide (DMAc) or ethanol, Organic solvents, such as isopropanol, can be used individually or in mixture.

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 when provided with a seal for forming a hollow therein, It may be a triple spinning nozzle or a quadruple spinning nozzle, and may be a triple spinning nozzle, a quadruple spinning nozzle, or a five-fold spinning nozzle when the internal coagulating solution injection unit is provided to form a hollow therein.

First, a multi-spinning nozzle having a closed portion formed therein for hollow formation will be described. FIG. 5 is a cross-sectional view of a double spinning nozzle 10 according to a preferred embodiment of the present invention. A first injection part 12 for forming single-layer metal hollow fiber on the outer circumferential surface of the center, and a polymer coating liquid for injecting the surface of the single-layer metal hollow fiber on the outer circumferential surface of the first injection part 12, A second injection unit 14 is provided, and a partition 13 for interlayer separation is formed between the first injection unit 12 and the second injection unit 14.

The size of the double spinning nozzle used can be appropriately formed according to the size of the metal hollow fiber to be manufactured, and the thickness of the partition wall is also thinner than the thickness of the partition wall of the conventional double spinning nozzle in order to improve the interlayer peeling force. It may be, preferably 0.5 to 3mm.

6 is a cross-sectional view of a triple spinning nozzle 20 in which a closed part is formed according to a preferred embodiment of the present invention. The first injection part 22 which forms the 1st layer of a two-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 part 26 is provided on the outer circumferential surface of the second injection part 24, and is formed for interlayer separation between the second injection part 24 and the third injection part 26. Two partitions 25 are formed.

Next, referring to the multi-spinning nozzle formed therein the internal coagulating liquid injection portion for forming the hollow, Figure 7 is a cross-sectional view of the triple spinning nozzle 300 according to a preferred embodiment of the present invention, the hollow hollow inside A first injection part 303 is formed on the outer circumferential surface around the inner coagulation liquid injection part 301 to be formed, and is formed between the internal coagulation liquid injection part 301 and the first injection part 303. One partition 302 may be provided. A second injection part 305 is provided on the outer circumferential surface of the first injection part 303 to provide a second separation between the first injection part 303 and the second injection part 305. The partition wall 304 is formed through which the single-layer hollow fiber precursor coated with the polymer may be radiated.

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. 8 is a cross-sectional view of the quadruple spinning nozzle 400. A third injection part 403 forming an inner layer of a two-layer hollow yarn on an outer circumferential surface of an inner coagulating liquid injection part 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 part 405 is formed on the outer circumferential surface of the third injection part 403 to form an outer layer of the two-layer hollow yarn, and an interlayer division is formed between the third injection part 403 and the first injection part 405. The first partition 404 is formed. A second injection unit 407 is provided on the outer circumferential surface of the first injection unit 405 to provide a second separation between the first injection unit 405 and the second injection unit 407. The partition 406 may be formed.

The coagulation bath for solidifying the metal hollow fiber precursor 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 May solidify rapidly and cause minor cracking in the precursor, and if it exceeds 70 ° C, the solvent vaporizes and is harmful to the body. Therefore, it is preferable to maintain the temperature of the water-based coagulation bath in the range of 0 to 70 ° C.

Next, in step (3), the metal hollow fiber precursor is treated at high temperature to oxidize the polymer binder and the coated polymer to prepare a metal hollow fiber precursor having porosity. Oxidation of the polymer means that the polymer binder and the coated polymer are burned off by heating to a high temperature, thereby forming pores in the oxidized portion of the polymer binder. The coated polymer also played a role of preventing warpage and protecting the surface of the metal hollow fiber precursor during the winding process, and since it should not be included in the final product, it is oxidized through the oxidation process.

The oxidation temperature is not limited as long as it can oxidize both the polymer binder and the coated polymer, preferably can oxidize the polymer at 300 ~ 700 ℃ and the oxidation time can be carried out for 0.5 to 3 hours but not limited thereto. It doesn't happen.

Next, as the step (4), the metal hollow fiber precursor sintered with the polymer binder and the coated polymer 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 as a conventional atmosphere alone or mixed in addition to the general air, nitrogen, argon, hydrogen and the like. Sintering time may be 1 to 4 hours.

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 >

The metal precursor solution was prepared by adding 8.6 parts by weight of polysulfone to 34.3 parts by weight of N-methyl-2-pyrrolidone as a polymer with respect to 100 parts by weight of nickel powder having an average particle diameter of 2.5 μm.

In addition, 25 parts by weight of polysulfone was dissolved in 100 parts by weight of N-methyl-2-pyrrolidone to prepare a polymer coating solution.

Water was injected into the internal coagulating liquid injection unit of the triple spinning nozzle of FIG. 7 having a diameter of 0.7 mm of the internal coagulation liquid injection unit and a diameter of the first injection unit 2.6 mm and a diameter of the second injection unit 3.2 mm. The metal precursor solution is injected, and the second injection portion is injected with a polymer coating solution and spun therein. The spun metal hollow fiber precursor is solidified in distilled water. Subsequently, the polymer hollow fiber precursor coated with the polymer was immersed in water for one day in a bobbin having a cylindrical winding having a diameter of 40 cm, and then removed through exchange of a solvent and water.

The metal hollow fiber precursor produced during the manufacturing process did not cause warpage or cutting.

It was then heated at 600 ° C. for 120 minutes to oxidize the polymer binder and the coated polymer. Thereafter, the metal particles were sintered in 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 Cooling to prepare a metal hollow fiber filter medium.

The surface of the prepared metal hollow fiber filter medium was very good in roughness.

<Example 2>

A metal hollow fiber filter medium was prepared in the same manner as in Example 1 except that a thermoplastic polystyrene-based elastomer (NUC-6170, Niuka, Japan) was used as a polymer for the coating solution.

As a result, there was no warpage or cut out of the metal hollow fiber precursor after bobbin winding and unwinding. In addition, the surface of the prepared metal hollow fiber filter medium was very good roughness.

<Example 3>

A metal hollow fiber filter medium was prepared in the same manner as in Example 1 except that polyimide was used instead of polysulfone as a polymer used in the coating solution.

As a result, there was no warpage or cut out of the metal hollow fiber precursor after bobbin winding and unwinding. In addition, the surface of the prepared metal hollow fiber filter medium was very good roughness.

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.

Claims (20)

(1) preparing a metal precursor solution by dispersing any one or more metal powders and polymer binders selected from the group consisting of transition metals, their oxides and alloys in a solvent;
(2) while simultaneously spinning the metal precursor solution and the polymer coating solution using the multi-radiation nozzle, injecting the polymer coating solution into the outermost injection portion of the multi-radiation nozzle so that the polymer coating solution can be coated on the surface of the metal hollow fiber precursor after spinning Preparing a metal hollow fiber precursor coated with a polymer;
(3) treating the polymer-coated metal hollow fiber precursor at a high temperature to oxidize the polymer binder and the coated polymer to produce a metal hollow fiber precursor having porosity; And
(4) sintering the metal hollow fiber precursor in which the polymer binder and the coated polymer are oxidized. The method of claim 1,
The polymer binder is a method for producing a metal hollow fiber filter medium, characterized in that the synthetic polymer is oxidized at the oxidation temperature of the step (3). 3. The method of claim 2,
The polymer binder is 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 polymer of the polymer coating solution is a method of manufacturing a metal hollow fiber filter medium to prevent the bending, characterized in that the material that can be pyrolyzed at the oxidation temperature of the step (3). 5. The method of claim 4,
The polymer of the polymer coating solution is a method of producing a metal hollow fiber filter medium to prevent the bending, characterized in that the material that can be pyrolyzed at 500 ℃ or less. The method of claim 1,
The polymer of the polymer coating solution may be any one or more selected from the group consisting of polysulfone, polyamide, polyolefin, polyimide, cellulose acetate, polyvinyl, polystyrene, polyether and thermoplastic elastomer. A method for producing a metal hollow fiber filter medium, characterized in that it prevents warping. The method according to claim 6,
The thermoplastic elastomer is a nylon elastomer, a silicone elastomer, a polyolefin elastomer, a PET elastomer, a polyurethane elastomer, a PVC elastomer manufacturing method of preventing metal hollow fiber filter material, characterized in that the elastomer. The method of claim 1,
Between (2) and (3) step of winding the metal hollow fiber precursor coated with the polymer in the bobbin and unwinding the method of manufacturing a metal hollow fiber filter medium to prevent the warp. The method of claim 1,
When the multi-spinning nozzle is provided with an internal coagulating solution injection unit for forming a hollow therein, the method of manufacturing the metal hollow fiber filter medium to prevent bending, characterized in that the triple spinning nozzle, quadruple spinning nozzle or five spinning nozzle. . The method of claim 1,
Wherein the multi-spinning nozzle is a method of manufacturing a metal hollow fiber filter medium to prevent bending, characterized in that the double spinneret, triple spinneret or quadruple spinneret when the seal is provided to form a hollow therein. The method of claim 1,
The transition metal is a method of producing a metal hollow fiber filter medium to prevent the warp, characterized in that the 3 to 5 cycle transition metal. 12. The method of claim 11,
The transition metal is nickel, titanium, aluminum, copper, iron and stainless steel, the method of manufacturing a metal hollow fiber filter medium to prevent bending, characterized in that any one. The method of claim 1,
The average particle diameter of the metal powder is 0.005 ~ 20 ㎛ characterized in that the manufacturing method of the metal hollow fiber filter medium to prevent the bending. The method of claim 1,
The solvent is a polar solvent, characterized in that the bending method for producing a metal hollow fiber filter medium. 15. The method of claim 14,
Wherein the polar solvent is any one or more selected from the group consisting of N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, 1-tridecanol and terpinol. Method of producing a metal hollow fiber filter medium to prevent. The method of claim 1,
The metal precursor solution of step (1) is a method for producing a metal hollow fiber filter medium to prevent bending, 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,
Method of producing a hollow fiber filter medium to prevent bending, characterized in that the thickness of the polymer coating layer of the step (2) is 0.1 ~ 500 ㎛. The method of claim 1,
Method of producing a multi-layer hollow fiber filter medium, characterized in that for 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 metal hollow fiber filter medium, characterized in that 700 ~ 1400 ℃. (1) preparing a metal precursor solution by dispersing any one or more metal powders and polymer binders selected from the group consisting of transition metals, their oxides and alloys in a solvent;
(2) while simultaneously spinning the metal precursor solution and the polymer coating solution using the multi-radiation nozzle, injecting the polymer coating solution into the outermost injection portion of the multi-radiation nozzle so that the polymer coating solution can be coated on the surface of the metal hollow fiber precursor after spinning Preparing a metal hollow fiber precursor coated with a polymer;
(3) treating the polymer-coated metal hollow fiber precursor at a high temperature to oxidize the polymer binder and the coated polymer to produce a metal hollow fiber precursor having porosity;
(4) preparing a metal hollow fiber filter medium by sintering the metal hollow fiber precursor in which the polymer binder and the coated polymer are oxidized; And
(5) mounting the metal hollow fiber filter medium in the vessel ballast water treatment apparatus; manufacturing method for a vessel ballast water treatment comprising a.

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