KR20170081001A - Method for manufacturing of ceramic hollow fiber membrane and the ceramic hollow fiber membrane thereby - Google Patents

Method for manufacturing of ceramic hollow fiber membrane and the ceramic hollow fiber membrane thereby Download PDF

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KR20170081001A
KR20170081001A KR1020150191563A KR20150191563A KR20170081001A KR 20170081001 A KR20170081001 A KR 20170081001A KR 1020150191563 A KR1020150191563 A KR 1020150191563A KR 20150191563 A KR20150191563 A KR 20150191563A KR 20170081001 A KR20170081001 A KR 20170081001A
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hollow fiber
fiber membrane
ceramic
spinning solution
nozzle
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KR1020150191563A
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Korean (ko)
Inventor
박호식
남승은
박유인
이평수
김여진
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한국화학연구원
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Publication of KR20170081001A publication Critical patent/KR20170081001A/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/02—Hollow fibre modules
    • B01D63/021—Manufacturing thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0039—Inorganic membrane manufacture
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/08—Hollow fibre membranes
    • B01D69/087—Details relating to the spinning process
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D1/00—Treatment of filament-forming or like material
    • D01D1/06—Feeding liquid to the spinning head
    • D01D1/065—Addition and mixing of substances to the spinning solution or to the melt; Homogenising
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/24—Mechanical properties, e.g. strength
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00—Physical properties
    • D10B2401/06—Load-responsive characteristics
    • D10B2401/063—Load-responsive characteristics high strength
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2505/00—Industrial
    • D10B2505/04—Filters

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Textile Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

The present invention relates to a process for producing a spinning solution by adding a polymer resin to a ceramic solution containing ceramic particles (step 1); (Step 2) of preparing a ceramic hollow fiber precursor by injecting the spinning solution prepared in step 1 into an extruder equipped with a screw, kneading and extruding the hollow fiber membrane precursor through a nozzle for producing a hollow fiber membrane into a coagulation bath containing a coagulant; And sintering the ceramic hollow fiber membrane precursor prepared in step 2 (step 3). The method of producing a ceramic hollow fiber membrane according to the present invention enables mass production using an extrusion method capable of applying high pressure and a phase transfer process and increases the mechanical strength by increasing the content of ceramic powder in a spinning solution . Particularly, even when the hollow fiber membrane is formed with the same ceramic content, excellent mechanical strength is obtained when the membrane is formed by the method according to the present invention.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a ceramic hollow fiber membrane and a ceramic hollow fiber membrane produced thereby,

The present invention relates to a method for producing a ceramic hollow fiber membrane and a ceramic hollow fiber membrane produced thereby.

Recently, separation membranes are attracting attention as a key element technology in various industrial fields such as water treatment, gas separation, petrochemical, electronic materials, medicine manufacturing, fuel cell, steam separation and the like. Membrane technology is defined as the technique of selectively separating certain components (one or more components) from a mixture of two or more components using a physical boundary layer. Currently, membrane technology has been widely applied in a wide range of applications ranging from simple laboratory scale to large-scale industry, in accordance with the social demand for the protection of the global environment, including the production of high-purity, highly functional materials and industrial wastewater treatment. Since the separation membrane process is a physical and mechanical separation operation that does not require a phase change, energy can be saved up to about 70% to 80% or more as compared with a conventional energy-less non-specific process, and the separation principle and process are relatively simple Thereby simplifying the configuration and installation of the apparatus and reducing the space occupied by the apparatus, thereby reducing the facility cost.

Particularly in the water treatment field, there is an active interest in increasing interest in environmentally friendly membrane separation processes, which are superior to existing physicochemical and biological processes and have improved water quality and use of chemicals.

Among the water treatment membranes, polymer membranes are widely used in most water treatment processes because they are easy to manufacture and have a low cost. However, they have poor thermal / chemical stability and low resistance to membrane contamination.

In this regard, there is growing interest in ceramic separators that can be used for a long time due to high chemical resistance, heat resistance, and durability under extreme conditions (high pressure, high temperature, acid / base, etc.)

As a method for synthesizing a ceramic hollow fiber membrane, an extrusion method is generally used, but the production speed is so slow that it is insufficient for use as a commercialization method.

In addition, a phase transfer method or the like has been utilized to synthesize a ceramic hollow fiber membrane. As a specific example, Korean Patent Laid-Open Publication No. 10-2013-0140396 discloses a method for producing a porous aluminum-based hollow fiber membrane and a linear porous aluminum-based hollow fiber membrane improved in mechanical strength and permselectivity. However, since the separation membrane still has a weak strength, its practical application is limited. Therefore, it is necessary to develop a separation membrane production method to overcome this problem.

An object of the present invention is to solve the problem that the production speed of the ceramic hollow fiber membrane production process is slow and the mechanical strength of the ceramic hollow fiber membrane to be produced is insufficient.

In order to achieve the above object,

Preparing a spinning solution by adding a polymer resin to a ceramic solution containing ceramic particles (step 1);

(Step 2) of preparing a ceramic hollow fiber precursor by injecting the spinning solution prepared in step 1 into an extruder equipped with a screw, kneading and extruding the hollow fiber membrane precursor through a nozzle for producing a hollow fiber membrane into a coagulation bath containing a coagulant; And

And sintering the ceramic hollow fiber membrane precursor prepared in step 2 (step 3).

In addition,

A spinning solution storage part for storing a spinning solution containing ceramic particles and a polymer resin;

An extruder connected to the spinning solution storage part and equipped with a screw; And

A first nozzle disposed at the very center; And a second nozzle disposed on an outer circumferential surface of the first nozzle. The present invention also provides an apparatus for manufacturing a ceramic hollow fiber membrane.

Further,

The present invention provides a water-treatment ceramic hollow fiber membrane produced by the above production method.

The method of producing a ceramic hollow fiber membrane according to the present invention enables mass production using an extrusion method capable of applying high pressure and a phase transfer process and increases the mechanical strength by increasing the content of ceramic powder in a spinning solution . Particularly, even when the hollow fiber membrane is formed with the same ceramic content, excellent mechanical strength is obtained when the membrane is formed by the method according to the present invention.

1 is a schematic view showing an example of an apparatus for producing a ceramic hollow fiber membrane according to the present invention.

The present invention

Preparing a spinning solution by adding a polymer resin to a ceramic solution containing ceramic particles (step 1);

(Step 2) of preparing a ceramic hollow fiber precursor by injecting the spinning solution prepared in step 1 into an extruder equipped with a screw, kneading and extruding the hollow fiber membrane precursor through a nozzle for producing a hollow fiber membrane into a coagulation bath containing a coagulant; And

And sintering the ceramic hollow fiber membrane precursor prepared in step 2 (step 3).

Hereinafter, the method for producing the ceramic hollow fiber membrane according to the present invention will be described in detail for each step.

First, in the method of manufacturing a ceramic hollow fiber membrane according to the present invention, step 1 is a step of preparing a spinning solution by adding a polymer resin to a ceramic solution containing ceramic particles.

In step 1, a raw material for producing a ceramic hollow fiber membrane by a phase transfer method is prepared, and a spinning solution is prepared by adding a polymer resin to a ceramic solution containing ceramic particles.

Specifically, the ceramic particles of step 1 may have a size of 0.1 μm to 10 μm, and may be in powder form. If the size of the ceramic particles of the step 1 is less than 0.1 탆, there is a problem of decreasing the permeability of the ceramic hollow fiber membrane to be formed. If the size of the ceramic hollow particles is more than 10 탆, the mechanical properties of the ceramic hollow fiber membrane are insufficient.

In addition, the ceramic particles in the step 1 are preferably 63 wt% to 90 wt%, more preferably 65 wt% to 85 wt%, and most preferably 70 wt% to 83 wt%, based on the total weight of the spinning solution. desirable. If the amount of the ceramic particles in the step 1 is less than 63% by weight based on the total weight of the spinning solution, there is a problem in that the mechanical strength of the hollow fiber membrane produced is insufficient due to insufficient content of the ceramic particles. The ceramic particles of the present invention have a remarkable decrease in the manufacturing process speed, which makes it impossible to mass-produce them.

Although the present invention encompasses a ceramic hollow particle having a content of 63 wt% or more, preferably 65 wt% or more, and more preferably 70 wt% or more, based on the total spinning solution weight, mass production of the ceramic hollow fiber membrane Easy, superior mechanical strength, and excellent water permeability.

The ceramic of step 1 may be selected from the group consisting of Group IA metals, Group IIA metals, Group IIIA A metals, Group IVA metals and transition metal oxides. For example, aluminum oxide (Al 2 O 3 ) (Al 2 (SO 4 ) 3 ), silicon dioxide (SiO 2 ), kaolinite (Al 2 Si 2 O 5 (OH) 4 ) and bentonite may be used alone or in combination.

Further, the polymer resin of step 1 may be selected from the group consisting of polysulfone, polyethersulfone, polyacrylate, polyacrylonitrile, polysulfide, polyketone, poly Polyetherketone, Polyetheretherketone, Polyimide, Polyamide, Polyamide-imide, Polyvinylidene fluoride, Polyethylene, Polypropylene, polyetherimide and polyvinylchloride, but it is more preferable to use polysulfone which is easily dissolved in a polar organic solvent. The polymer resin serves as a binder before sintering in a spinning solution containing a ceramic powder.

The polymer resin of step 1 is preferably added in an amount of 2 to 8 wt% based on the total weight of the spinning solution. If the polymer resin of step 1 is added in an amount of less than 2% by weight, it may have a problem that it acts as a binder. If the polymer resin is added in an amount of more than 8% by weight, the viscosity of the solution becomes too large.

Further, in step 1, a sintering aid such as yttria (Y 2 O 3 ), magnesium oxide (MgO) and a dispersant such as BYK-190 may be added. The sintering aid enhances the mechanical strength of the hollow fiber membrane by increasing the sintering speed of the hollow fiber membrane, and the dispersing agent serves to uniformly distribute the aluminum precursor in the polar organic solvent.

The spinning solution of step 1 may further include a polar organic solvent. Examples of the polar organic solvent include N-methyl pyrrolidone (NMP), 1-methyl-2-pyrrolidone, dimethylformamide, dimethyl It is preferable to use acetamide, dimethylformaldehyde, dimethylsulfoxide, trimethylphosphate, triethylphosphate or the like, but it is more preferable to use N-methylpyrrolidone which has a high solubility and a high boiling point and is advantageous in terms of stability in spinning .

Next, in the process for producing a ceramic hollow fiber membrane according to the present invention, step 2 is carried out by kneading the spinning solution prepared in step 1 into an extruder equipped with a screw and kneading the coagulant through a nozzle for producing a hollow fiber membrane To thereby produce a ceramic hollow fiber precursor.

The step 2 is a step of preparing a ceramic hollow fiber precursor by performing an extrusion process using a spinning solution prepared for the phase transformation step, and in particular, by extruding the ceramic hollow fiber membrane precursor with a coagulation bath using an extruder equipped with a screw, .

Generally, in order to perform the phase transformation step, a spinning solution is prepared, and then a deaeration process is performed to remove impurities such as air dissolved in the spinning solution. Due to this degassing process, the ceramic powder in the uniformly mixed spinning solution may sink due to gravity or aggregation between the ceramic particles may occur. However, in the step 2 of the present invention, there is an advantage that it is not necessary to carry out a separate degassing process by using an extruder equipped with a screw, since the kneading and extrusion proceed simultaneously.

Specifically, the extrusion of step 2 is preferably carried out at a pressure of 10 bar to 50 bar, more preferably at a pressure of 12 bar to 45 bar. If the extrusion of the step 2 is carried out at a pressure of less than 10 bar, the packing density of the ceramic powder due to the decrease of the discharge amount is low and the separator does not have sufficient strength to be applied to the water treatment process. There is a problem that the ceramic powder as the main material of the separation membrane is excessively contained and it is difficult to extrude or the extrusion speed is remarkably reduced to lower the productivity.

In addition, although the shape of the nozzle for manufacturing the hollow fiber membrane in the step 2 is not particularly limited, the nozzle may include a first nozzle provided at the very center of the nozzle; And a second nozzle provided on an outer circumferential surface of the first nozzle.

At this time, it is preferable that a coagulant and a spinning solution are injected into the double nozzle, a coagulant is injected into the first nozzle, and a spinning solution is injected into the second nozzle.

As the coagulant of step 2, a non-solvent is generally used, but a mixed solvent in which a poor solvent, a good solvent or the like is mixed or a low molecular weight organic material is mixed may be used. In addition, the coagulation bath contains a non-solvent, preferably water, as a coagulant, and the temperature of the coagulant stored in the coagulation bath is preferably 0 to 80 ° C, but is not limited thereto.

Next, in the method of manufacturing a ceramic hollow fiber membrane according to the present invention, step 3 is a step of sintering the ceramic hollow fiber membrane precursor produced in step 2 above.

In step 3, the ceramic hollow fiber membrane precursor prepared in steps 1 and 2 is sintered to finally produce a ceramic hollow fiber membrane.

At this time, the ceramic hollow fiber precursor may be post-treated before the sintering of the ceramic hollow fiber membrane precursor of step 3 to remove the solvent and impurities to stabilize the ceramic hollow fiber membrane precursor.

Specifically, the post-treatment may be performed at room temperature for 12 hours to 72 hours, and may be performed for 24 hours to 48 hours, but is not limited thereto. The hollow fiber membrane precursor prepared through the above step 2 may contain a solvent and free impurities in the hollow fiber membrane precursor, and thus the hollow fiber membrane precursor may exhibit an unstable state. Therefore, a hydrothermal treatment step may be performed to remove the solvent and impurities while stabilizing the separation membrane.

Further, the method may further include washing the ceramic hollow fiber membrane precursor with an aqueous alcohol solution before sintering the ceramic hollow fiber membrane precursor of the step 3. At this time, the alcohol concentration of the alcohol aqueous solution may be 10 wt% to 20 wt%, and the alcohol may be methanol, ethanol, propanol, or the like.

Further, the sintering of step 3 may be performed at a temperature of 1300 ° C to 1600 ° C for 1 hour to 10 hours. If the sintering temperature of step 3 is less than 1300 ° C, the physical properties of the ceramic hollow fiber membrane to be formed are deteriorated. If the sintering temperature is higher than 1600 ° C, particle growth occurs and the permeability is reduced. If the sintering time is less than 1 hour, the sintering is not sufficiently performed, and the physical properties of the porous hollow fiber membrane deteriorate. If the sintering time exceeds 10 hours, there is no further sintering effect, which is not economical.

In addition,

A spinning solution storage part for storing a spinning solution containing ceramic particles and a polymer resin;

An extruder connected to the spinning solution storage part and equipped with a screw; And

A first nozzle disposed at the very center; And a second nozzle disposed on an outer circumferential surface of the first nozzle. The present invention also provides an apparatus for manufacturing a ceramic hollow fiber membrane.

Here, an example of the apparatus for producing a ceramic hollow fiber membrane according to the present invention is shown in the schematic view of FIG. 1,

Hereinafter, an apparatus for producing a ceramic hollow fiber membrane according to the present invention will be described in detail with reference to the schematic diagram of FIG.

Generally, when the ceramic hollow fiber membrane is manufactured by the phase transfer method, when the ceramic particle content in the spinning solution exceeds 60 wt% based on the total spinning solution weight, spinning is difficult and problems occur in the hollow fiber membrane formation itself.

However, the apparatus for producing a ceramic hollow fiber membrane according to the present invention is an apparatus for producing a ceramic hollow fiber membrane by simultaneously performing a phase transition step and an extrusion step, wherein the ceramic particle content is 63 wt% Is not less than 65% by weight, more preferably not less than 70% by weight, or more, the ceramic hollow fiber membrane is easily mass-produced, has excellent mechanical strength, and exhibits excellent water permeability as well.

Specifically, in the apparatus 10 for producing a ceramic hollow fiber membrane according to the present invention, the spinning solution storage part 1 stores a spinning solution containing ceramic particles and a polymer resin.

The spinning solution storage part 1 is connected to an extruder 2 equipped with a screw, and the extruder moves the spinning solution flowing through the spinning solution storage part to the nozzle 3, Radiate.

At this time, the extruder 2 is equipped with a screw, and it is possible to perform high-pressure extrusion simultaneously with kneading through rotation of the screw. Generally, in order to perform the phase transformation step, a spinning solution is prepared and then a deaeration process is performed to remove impurities such as air dissolved in the spinning solution. Due to this degassing process, the ceramic powder in the uniformly mixed spinning solution may sink due to gravity or aggregation between the ceramic particles may occur. However, the apparatus for producing a ceramic hollow fiber membrane of the present invention has an advantage that an extruder equipped with a screw is included, so that it is not necessary to perform a separate degassing process by progressing extrusion along with kneading.

In addition, although the shape of the nozzle 3 is not particularly limited, a first nozzle provided at the very center of the nozzle; And a second nozzle provided on an outer circumferential surface of the first nozzle.

At this time, the ceramic hollow fiber membrane production apparatus 10 may further include a coagulant storage unit 5 and a pump 6, which are connected to the first nozzle and store the coagulant. Specifically, a coagulant is injected into the first nozzle provided at the very center of the nozzle, and the spinning solution can be injected into the second nozzle provided on the outer circumferential surface of the first nozzle.

The coagulation bath 4 includes a coagulant. As the coagulant, a non-solvent is generally used. In some cases, a mixed solvent in which a poor solvent, a good solvent or the like is mixed or a low molecular weight organic material is mixed may be used. Preferably, water is stored in the coagulation bath, and the temperature of the coagulant stored in the coagulation bath is preferably 0 ° C to 80 ° C, but is not limited thereto.

Further, the ceramic hollow fiber membrane production apparatus 10 may further include a bobbin 8 for forming and recovering a ceramic hollow fiber membrane produced by spinning or extruding into a hollow fiber, and further, The desert production apparatus may further include a control unit (7) for controlling the production apparatus.

Further,

The present invention provides a water-treatment ceramic hollow fiber membrane produced by the above production method.

The ceramic hollow fiber membrane according to the present invention is manufactured by using an extrusion method capable of high pressure application together with a phase transfer process. Thus, the ceramic hollow fiber membrane has excellent mechanical strength and excellent water permeability.

Particularly, when the hollow fiber membrane is formed with the same ceramic content, the ceramic hollow fiber membrane formed by the method according to the present invention has an effect of exhibiting excellent mechanical strength.

The inner diameter of the water-treatment ceramic hollow fiber membrane may be 0.5 mm to 2.1 mm, the outer diameter may be 0.9 mm to 3 mm, and may have a straight line shape.

Hereinafter, the present invention will be described in detail with reference to the following examples and experimental examples.

However, the following Examples and Experimental Examples are merely illustrative of the present invention, and the present invention is not limited by the following Examples and Experimental Examples.

Example 1 Production of ceramic hollow fiber membrane 1

Step 1: 70% by weight of aluminum powder (Al 2 O 3 ) having an average particle size of 1.1 μm, 1.5% by weight of BYK-190, 0.5% by weight of magnesium oxide, 2% by weight of polyethylene glycol and 6% And 20% by weight of pyrrolidone were dispersed and mixed by stirring for 24 hours to prepare a spinning solution.

Step 2: The spinning solution prepared in step 1 is continuously extruded (50 bar) using a Kneading Vacuum Extrusion Molding Machine (FM-P20, Miyazaki Iron Works Co., Ltd.), a nozzle and a winder After solidifying with water as a coagulant, the ceramic hollow fiber membrane precursor was prepared by washing in water at room temperature for 48 hours. The washed hollow fiber membrane precursor was treated with a 20% aqueous ethanol solution for 24 hours to remove residual organic solvent additive and impurities.

Step 3: The ceramic hollow fiber membrane precursor prepared in step 2 was placed in an electric furnace and sintered at a temperature of 1450 ° C for about 3 hours to prepare a porous aluminum-based hollow fiber membrane.

≪ Comparative Example 1 &

Step 1: 70 wt% of aluminum powder (Al 2 O 3 ) having an average particle size of 1.1 μm, 1.5 wt% of BYK-190 and 0.5 wt% of magnesium oxide were mixed with 20 wt% of N-methylpyrrolidone and 2 wt% And 6% by weight of polysulfone were dispersed and mixed by stirring for 24 hours to prepare a spinning solution. The aluminum precursor solution was then degassed under vacuum at 50 < 0 > C for 24 hours prior to the phase transformation process.

Step 2: A porous aluminum-based hollow fiber membrane was prepared through the phase transformation process of the spinning solution prepared in step 1 above. Specifically, the temperature of the spinning apparatus was maintained at 70 ° C., and the spinning solution was maintained at a constant viscosity. The spinning was performed at 7 bar by using nitrogen gas, and then phase transformation was performed using water as an internal coagulant and external coagulant. The discharged hollow fiber membrane was stored in water at room temperature for 24 hours and then washed. The washed hollow fiber membrane was hydrothermally treated with hot water at 80 ° C for 6 hours to remove organic solvent additives and impurities remaining in the hollow fiber membrane. The hydrothermally treated hollow fiber membrane was placed in an electric furnace and sintered at 1450 ° C for 2 hours to prepare a porous aluminum hollow fiber membrane.

Experimental Example 1 Analysis of water permeability and mechanical strength of ceramic hollow fiber membrane

In order to confirm the water permeability and the mechanical strength of the ceramic hollow fiber membrane produced by the method of manufacturing the ceramic hollow fiber membrane according to the present invention, the water permeability according to pressure was measured using the ceramic hollow fiber membrane manufactured in Example 1 and Comparative Example 1 The total amount was measured by a filtration method using a water permeation device, and the bending strength was measured. The results are shown in Table 1 below.

Water permeability (LMH, 1 bar) Mechanical strength (MPa) Example 1 776.5 134 Comparative Example 1 754.7 95

As shown in Table 1, it was confirmed that the ceramic hollow fiber membrane produced by the manufacturing method according to the present invention had a water permeability of 776.5 LMH and a mechanical strength of 134 MPa.

On the other hand, in the case of the ceramic hollow fiber membrane produced by a general phase transfer process, the water permeability is somewhat similar to 754.7 LMH, but it is confirmed that the mechanical strength is remarkably insufficient at 95 MPa.

As described above, the ceramic hollow fiber membrane produced by the production method according to the present invention exhibits remarkably excellent mechanical strength despite being manufactured using the same amount of ceramic powder.

10: Ceramic hollow fiber membrane manufacturing equipment
1: spinning solution storage part 2: extruder
3: nozzle 4: coagulation tank
5: coagulant storage part 6: pump
7: control unit 8: bobbin
9: Ceramic hollow fiber membrane

Claims (10)

Preparing a spinning solution by adding a polymer resin to a ceramic solution containing ceramic particles (step 1);
(Step 2) of preparing a ceramic hollow fiber precursor by injecting the spinning solution prepared in step 1 into an extruder equipped with a screw, kneading and extruding the hollow fiber membrane precursor through a nozzle for producing a hollow fiber membrane into a coagulation bath containing a coagulant; And
And sintering the ceramic hollow fiber membrane precursor prepared in step 2 (step 3).
The method according to claim 1,
Wherein the ceramic particles of step 1 are present in an amount of 63 wt% to 90 wt% with respect to the total weight of the spinning solution.
The method according to claim 1,
Wherein the ceramic of step 1 is one oxide selected from the group consisting of Group IA metals, Group IIA metals, Group IIA metals, Group IVA metals, and transition metals.
The method according to claim 1,
The polymer resin of step 1 may be selected from the group consisting of polysulfone, polyethersulfone, polyacrylate, polyacrylonitrile, polysulfide, polyketone, Polyetheretherketone, polyetheretherketone, polyimide, polyamide, polyamide-imide, polyvinylidene fluoride, polyethylene, poly Wherein the at least one selected from the group consisting of polypropylene, polyetherimide, and polyvinylchloride is at least one selected from the group consisting of polypropylene, polyetherimide, and polyvinylchloride.
The method according to claim 1,
Wherein the polymer resin of step 1 is added in an amount of 2 wt% to 8 wt% based on the total weight of the spinning solution.
The method according to claim 1,
Wherein the extrusion of step 2 is performed at a pressure of 10 bar to 50 bar.
The method according to claim 1,
In the nozzle for producing the hollow fiber membrane of the step 2,
A first nozzle provided at the very center of the nozzle; And
And a second nozzle provided on an outer circumferential surface of the first nozzle.
8. The method of claim 7,
Injecting a coagulant into the first nozzle,
And a spinning solution is injected into the second nozzle.
A spinning solution storage part for storing a spinning solution containing ceramic particles and a polymer resin;
An extruder connected to the spinning solution storage part and equipped with a screw; And
A first nozzle disposed at the very center; And a second nozzle disposed on an outer circumferential surface of the first nozzle.
A ceramic hollow fiber membrane produced by the method of claim 1.
KR1020150191563A 2015-12-31 2015-12-31 Method for manufacturing of ceramic hollow fiber membrane and the ceramic hollow fiber membrane thereby KR20170081001A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102117957B1 (en) * 2019-01-16 2020-06-09 성균관대학교산학협력단 Conductive polymeric hollow fiber and preparing method thereof
WO2022102824A1 (en) * 2020-11-13 2022-05-19 (주)선진환경 Apparatus for manufacturing hollow fibers

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102117957B1 (en) * 2019-01-16 2020-06-09 성균관대학교산학협력단 Conductive polymeric hollow fiber and preparing method thereof
WO2022102824A1 (en) * 2020-11-13 2022-05-19 (주)선진환경 Apparatus for manufacturing hollow fibers

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