KR101355017B1 - Highly efficient hollow fiber membranes and manufacturing method thereof - Google Patents

Abstract

The present invention relates to a high-performance hollow fiber membrane and a manufacturing method thereof. The hollow fiber membrane according to the present invention is a membrane composed of polyvinylidene fluoride resin having an outer pore layer in the shape of sponge without macrovoid combined with an inner support layer to have two layers while exfoliation is minimized owing to excellent adhesion between the layers. The outer pore layer in the shape of sponge without macrovoid realizes a high rejection rate and high water permeation because the outer pore layer is porous while being in the shape of sponge. In addition, the present invention realizes excellent mechanical properties by forming the inner support layer in the process of increasing the concentration of polyvinylidene fluoride resin as the mixed solvent of benzenedicarboxylic acid and an alkyl ester, wherein the optimized mixture ratio of the good solvent and the non-solvent is used. In addition, the hollow fiber membrane according to the present invention can be applied to pretreatment for seawater desalination, water purification, wastewater treatment, and concentration and purification.

Description

High Performance Hollow Fiber Membrane and Its Manufacturing Method {HIGHLY EFFICIENT HOLLOW FIBER MEMBRANES AND MANUFACTURING METHOD THEREOF}

The present invention relates to a high performance hollow fiber membrane and a method of manufacturing the same, and more particularly, to a membrane made of a polyvinylidene fluoride resin having a macroporous sponge-like outer pore layer and an inner support layer bonded together, Which is excellent in mechanical properties with high rejection and water permeability, and a method for producing the same.

Due to industrialization and urbanization all over the world, not only the water shortage but also the demand for industrial wastewater and domestic sewage treatment facilities are rapidly increasing. In particular, there is a demand for a method of using the water as a drinking water by purifying the river by the lack of water to eat.

In accordance with this demand, studies on separation membranes used in water treatment and wastewater treatment have been actively carried out. Particularly, in the case of hollow membrane membranes, since they have high permeability while completely removing pathogenic microorganisms, energy is reduced and high strength And thus it is in the spotlight because it has stability of operation.

In order to realize such a performance, the hollow fiber separator should be chemically stable by using a fluorine resin in terms of materials and minimize the defect by minimizing the thickness of the active layer in terms of performance.

A separation membrane having a multilayer structure has been attempted to be manufactured by physically bonding a layer capable of maintaining strength and a layer capable of controlling pore size separately. For example, Korean Patent No. 966718 discloses a porous multi-layered hollow fiber membrane which is suitable for filtration and has high pore water permeability and high permeability while exhibiting a high strength. However, the problem of peeling off during backwashing due to weak physical bonding force between layers . Therefore, it is necessary to manufacture a membrane having high physical binding force.

Examples of the polymer resin capable of producing a separator include fluorine-based polymers such as polyvinylidene fluoride, sulfonic polymers such as polyethersulfone, imide polymers such as polyetherimide, cellulosic polymers such as cellulose acetate, polyacrylonitrile Based polymer such as polyvinylidene fluoride, which is resistant to chlorine, is preferably used.

The solvent capable of dissolving the polymer resin has been mainly used as a solvent that can be dissolved at room temperature. However, when the concentration of the polymer is high, there is a limit to increase the concentration of the polymer resin due to the viscosity thereof.

Therefore, in recent years, a solvent which can dissolve only when the temperature is elevated is used in addition to such a solvent, which is defined as a poor solvent. That is, when the temperature is raised to near the melting point of the polymer resin, the poor solvent to be dissolved can increase the viscosity to a level that can be molded even if the concentration of the polymer resin is increased, and the strength of the hollow fiber separator can be increased.

Korean Patent No. 904943 discloses a polyvinylidene fluoride resin composition which contains a polyvinylidene fluoride resin and a poor solvent of the resin and discharges the polyvinylidene fluoride resin solution whose temperature is the phase separation temperature or higher to a cooling bath below the phase separation temperature, Desert is known.

In the present invention, the poor solvent used in producing the hollow fiber membrane is selected from cyclohexanone, isophorone,? -Butyrolactone, and dimethyl phthalate. Therefore, cyclic ketones such as cyclohexanone and aromatic phthalates such as dimethyl phthalate are usually used. However,

The present inventors have made efforts to improve the membrane performance so as to be applicable to seawater desalination pretreatment, water treatment, underwater treatment, wastewater treatment and concentration and refining. As a result, it has been found that, by using a special injection nozzle, And the inner supporting layer is formed with a specific solvent condition or a specific injection nozzle so that a high rejection rate and a high water permeability can be obtained by forming the outer pore layer and the inner supporting layer, And confirming the physical properties of the separator having excellent mechanical properties, thereby completing the present invention.

An object of the present invention is to provide a high performance hollow fiber membrane having a high rejection rate and a water permeability and excellent mechanical properties.

Another object of the present invention is to provide a method for producing the high performance hollow fiber membrane.

It is a further object of the present invention to provide a novel poor solvent composition for the production of hollow fibers.

The present invention provides a hollow fiber membrane made of a polyvinylidene fluoride resin, to which a sponge-like outer pore layer free from macrovoids and an inner support layer are bonded.

At this time, in the hollow fiber membrane of the present invention, the outer pore layer has a thickness of 5 to 100 mu m and a pore size of 0.01 to 0.08 mu m.

In the hollow fiber separator of the present invention, the inner supporting layer is formed to a thickness of 100 to 600 mu m.

In the hollow fiber membrane of the present invention, distilled water at a temperature of 20 ° C is introduced into the hollow, and the permeation flow rate is measured while the pressure is increased. The separation pressure at which the permeation flow rate instantaneously increases is 8 to 15 bar.

The hollow fiber membrane of the present invention has a tensile strength of 0.4 to 2.0 MPa and an elongation of 5 to 120% and satisfies 400 to 1200 L / m 2 hr at a water permeability of 1 kgf / cm 2 of the hollow fiber membrane, And has excellent mechanical properties.

The present invention relates to a process for preparing a spray nozzle, comprising: 1) transferring a dope solution for forming a support layer containing 30 to 60% by weight of polyvinylidene fluoride and 40 to 70% by weight of a mixed solvent obtained by mixing a good solvent and a non-

2) a porous layer forming dope containing 5 to 20% by weight of polyvinylidene fluoride, 20 to 60% by weight of a good solvent, 20 to 40% by weight of benzene dicarboxylic acid alkyl ester and 15 to 20% The solution is transferred to the spray nozzle outer layer,

3) In order to form the transferred coating solution into a hollow form, it is transferred to a hollow forming injection nozzle,

4) The spinning is followed by immersion in an external coagulating bath to effect phase transformation and drying.

In the production method of the present invention, the mixed solvent is composed of a good solvent and a non-solvent, and is mixed in a weight ratio of the following (1).

Positive solvent / (positive solvent + non-solvent) ≤ 0.2 (1)

At this time, two-way tie dimethylacetamide, dimethylformamide, N- methyl-2-pyrrolidone and money and dimethyl sulfoxide alone or a mixture of two or more selected from the group consisting of, cost tying benzene dicarboxylic acid, C ₁ ~ _C12 alkyl ester.

In particular, the positive solvent of step 1) and the two solvents of step 2) are used as solvents of the same composition to form the inner support layer and the outer pore layer, thereby providing peel stability to the interlayer-bonded separator.

In the production method of the present invention, the transfer line length of the pore layer-forming dope solution of the injection nozzle of step 2) is 1/3 to 1/10 of the transfer line length of the dope solution for forming the support layer of the injection nozzle of step 1) .

The dope solution for forming the support layer is sprayed from the injection nozzle of the step 1) to form the support layer, and the dope solution for forming the pore layer is sprayed from the injection nozzle of the step 2), and the pore layer is coated on the support layer will be.

In the above, the supporting layer forming dope solution is sprayed at 120 to 200 ° C to form a supporting layer, and the pore layer forming dope solution is sprayed at 20 to 120 ° C to form a pore layer.

Further, the present invention relates to a poor solvent composition for the hollow fiber preparation in which the non-colvent of the good solvent and the alkyl ester of the benzene dicarboxylic acid C ₁ -C ₁₂ are mixed in the following weight ratio (1) .

Positive solvent / (positive solvent + non-solvent) ≤ 0.2 (1)

In the above, both of them are a single or a mixture of two or more selected from the group consisting of dimethylacetamide, dimethylformamide, N-methyl-2-pyrrolidone and dimethylsulfoxide.

The high performance hollow fiber membrane according to the present invention can maintain a high water permeability and the high molecular weight can be continuously connected to the microorganism and the virus.

The high performance hollow fiber membrane of the present invention can be used for pretreatment of seawater desalination, water treatment, under treatment, wastewater treatment, concentration and purification.

1 is a cross-sectional view of a hollow fiber membrane according to the present invention,
Fig. 2 is a cross-sectional side view of the hollow fiber membrane according to the present invention.

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

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a cross-sectional view of a hollow fiber membrane according to the present invention. And

And a hollow support membrane composed of a polyvinylidene fluoride resin combined with an inner support layer.

The hollow fiber membrane of the present invention has a structure in which two layers having different characteristics are combined and interlayer bonded due to the same solvent in each layer forming solution.

FIG. 2 is a cross-sectional side view of the hollow fiber membrane according to the present invention. In the hollow fiber membrane of the present invention, the cross-sectional structure of the porous layer formed on the outer side of the separation membrane is a sponge- .

At this time, the outer pore layer has a sponge shape and a porosity of 0.01 to 0.08 탆 pore size, thereby realizing a high rejection rate and water permeability.

In the specification of the present invention, the macrovoid refers to a hole shape formed in a cross-section of a separation membrane with a finger-like structure, and typically has a pore size of 0.2 μm. When the macro-void type and size pore structure are formed in the outer pore layer of the separator, there is a problem that the strength of the separator is reduced, large pores are formed with large surface pores and defects on the surface, and pores are piled up due to accumulation of contaminants.

On the other hand, in the hollow fiber membrane of the present invention, the outer pore layer is formed to a thickness of 5 to 100 mu m and is formed into a sponge shape having a pore size of 0.01 to 0.08 mu m without macrovoid. At this time, if the thickness of the outer pore layer is less than 5 mu m, there is a problem that the strength of the pore layer is weak and it may pop up during the backwashing process, and when it exceeds 100 mu m, the permeation flow rate is decreased.

In the hollow fiber membrane of the present invention, the inner supporting layer is formed to a thickness of 100 to 600 탆. If the thickness of the strength layer is less than 100 탆, There is a difficulty in decreasing the module flow rate due to the reduced thickness of the membrane area during module manufacture.

The hollow fiber membrane of the present invention is capable of removing pathogenic microorganisms and viruses while maintaining high water permeability and satisfying physical properties with excellent mechanical properties.

Specifically, when the permeation flow rate is measured while increasing the pressure by introducing distilled water at 20 ° C inside the hollow, and the pressure at which the permeation flow rate instantaneously rises is regarded as the separation pressure, the separation pressure of the present invention is 8 to 15 bar to be.

The hollow fiber membrane of the present invention has a tensile strength of 0.4 to 2.0 MPa and an elongation of 5 to 120% and satisfies 400 to 1200 L / m 2 hr at a water permeability of 1 kgf / cm 2 of the hollow fiber membrane, And it can be confirmed that the mechanical properties are excellent.

The present invention provides a method for producing a hollow fiber membrane having a high rejection ratio and a water permeation tank and excellent mechanical properties. More specifically,

1) A dope solution for forming a support layer containing 30 to 60% by weight of polyvinylidene fluoride and 40 to 70% by weight of a mixed solvent obtained by mixing a good solvent and a non-solvent is transferred to the inner layer of the injection nozzle,

2) a porous layer forming dope containing 5 to 20% by weight of polyvinylidene fluoride, 20 to 60% by weight of a good solvent, 20 to 40% by weight of benzene dicarboxylic acid alkyl ester and 15 to 20% The solution is transferred to the spray nozzle outer layer,

3) In order to form the transferred coating solution into a hollow form, it is transferred to a hollow forming injection nozzle,

4) after the spinning, immersing in an external coagulating bath to effect phase transformation and drying.

In the method of manufacturing a hollow fiber membrane of the present invention, the dope solution is injected through different paths to form two layers having different characteristics of the support layer and the pore layer, and the injection nozzle is optimized so that the outer pore layer And the inner supporting layer are formed by using the same solvent, the interlayer bonding force between the pore layer and the supporting layer is increased.

In addition, by forming the cross-sectional structure of the pore layer in the form of a sponge without macrovoids, a high water permeability is achieved while maintaining a small pore size.

The polyvinylidene fluoride, which is a polymer resin used in the method for producing a hollow fiber membrane of the present invention, includes a vinylidene fluoride homopolymer and a vinylidene fluoride copolymer.

In the method for producing a hollow fiber membrane of the present invention, in the step 1), the doping solution for forming the support layer contains 30 to 60% by weight of polyvinylidene fluoride and 40 to 70% by weight of a mixed solvent obtained by mixing a good solvent and a non-solvent.

At this time, in order to maintain the high strength of the support layer, the concentration of polyvinylidene fluoride should be kept high, and even if the temperature is raised, the viscosity is maintained so as to be formed into a hollow fiber. Therefore, even if it can not be melted at room temperature, a poor solvent which can be melted at a high temperature is used.

Accordingly, in the present invention, a mixed solvent in which both a solvent and a non-solvent are mixed is used as a new poor solvent without using a poor solvent used in the conventional literature.

In this case, the mixed solvent of the positive solvent of the present invention and the non-solvent is mixed in the weight ratio of the following (1).

Positive solvent / (positive solvent + non-solvent) ≤ 0.2 (1)

The mixed solvent may be a mixture of two or more selected from the group consisting of dimethylacetamide, dimethylformamide, N-methyl-2-pyrrolidone, and dimethylsulfoxide, use of benzene dicarboxylic acid esters of C ₁ ~C _12.

At this time, it is preferable that the weight ratio of the positive solvent / (positive solvent + non-solvent) is 0.2 or less. If the positive solvent / (positive solvent + non-solvent) exceeds 0.2, the viscosity increases sharply, it's difficult.

By using the alkyl ester of benzene dicarboxylic acid C ₁ -C ₁₂ as a non-solvent in the mixed solvent of the present invention, flexibility of the hollow fiber, which is generally used as a plasticizer, is increased, and when mixed with both solvents, And serves as a poor solvent.

The polyvinylidene fluoride used in the dope solution for forming the support layer in step 1) is preferably contained in a proportion of 30 to 60% by weight. If the content of polyvinylidene fluoride is less than 30% by weight, the strength is lowered. If the content is more than 60% by weight, the viscosity is excessively increased.

In the method for producing a hollow fiber membrane of the present invention, in the step 2), the dope solution for forming a pore layer may contain 5 to 20% by weight of polyvinylidene fluoride, 20 to 60% by weight of a good solvent, 40% by weight and porosity forming agent 15 - 20% by weight.

When the dope solution contains less than 5% by weight of polyvinylidene fluoride, there is a problem that the viscosity is too low to coat the coating, while when it exceeds 20% by weight, the water permeability is drastically reduced.

If the two solvents are contained in an amount of less than 20% by weight, it is difficult to dissolve the polymer. When the amount of the two solvents is more than 60% by weight, macrovoids are formed.

When the benzene dicarboxylic acid alkyl ester content is less than 20% by weight, macrovoids are formed. When the benzene dicarboxylic acid alkyl ester content is more than 40% by weight, there is a problem that it is difficult to dissolve the polymer.

It is preferable to use polyethylene glycol, polyvinyl pyrrolidone or a mixture thereof. If the content is less than 15% by weight, the water permeability decreases. When the content exceeds 20% by weight, the viscosity increases sharply, there is a problem.

The dope solution for forming the pore layer may contain additives which are usually used in the production of the hollow fiber membrane.

Since the dope solution for forming the pore layer and the dope solution for forming the support layer are chemically bonded using the same solvent in the solution, the peeling phenomenon between the formed pore layer and the support layer can be minimized.

The two kinds of the dope solutions prepared above are introduced into the injection nozzles of the respective channels and radiated to form the support layer and the pore layer.

In this case, the injection nozzle is preferably such that the transfer line length of the dope solution for forming the pore layer of the injection nozzle in step 2) is 1/3 to 1/10 of the transfer line length of the dope solution for forming the support layer of the injection nozzle of step 1) desirable.

If the length of the transfer line of the dope solution for forming the pore layer exceeds 1/3 of the length of the transfer line of the dope solution for forming the pore layer, the pore layer doping solution is cooled in the injection nozzle to clog the nozzle, If the length is less than 1/10, there is a problem that the contact time is short and coating is not easy.

Further, a support layer is formed by spraying the support layer-forming solution from the injection nozzle in the step 1), and a dope solution for forming a pore layer is sprayed from the injection nozzle of the step 2), and a pore layer is coated on the support layer will be.

In the above, the support solution for forming the support layer is sprayed at 120 to 200 DEG C to form the support layer. If the temperature is lower than 120 ° C, there is a problem that the dope solution becomes solidified and the nozzle is clogged. On the other hand, when the temperature exceeds 200 ° C, vaporization of the solvent occurs and the viscosity increases sharply.

On the other hand, the pore layer forming dope solution is sprayed at 20 to 120 캜 to form a pore layer. At this time, if the temperature is lower than 20 ° C, the solid becomes solidified and the nozzle becomes clogged. If it exceeds 120 ° C, the viscosity becomes too low and coating is not easy.

In the method for producing a hollow release membrane of the present invention, when the temperature of the dope solution for forming a pore layer is low, delamination occurs. When the temperature is high, the separation pressure increases but the pore size becomes large.

In order to solve this problem, the present invention is to change the composition of the dope solution for forming the pore layer, more specifically, to use the same solvent used in the dope solution for forming the support layer, more preferably increase the content of the same solvent So that they can be mixed chemically.

In the method for producing a hollow fiber membrane of the present invention, the external coagulating bath of step 4) is preferably water or isopropanol.

Further, the present invention relates to a poor solvent composition for the hollow fiber preparation in which the non-colvent of the good solvent and the alkyl ester of the benzene dicarboxylic acid C ₁ -C ₁₂ are mixed in the following weight ratio (1) .

Positive solvent / (positive solvent + non-solvent) ≤ 0.2 (1)

In the above, both of them are a single or a mixture of two or more selected from the group consisting of dimethylacetamide, dimethylformamide, N-methyl-2-pyrrolidone and dimethylsulfoxide.

The novel poor solvent of the present invention is a form obtained by reacting a small amount of a good solvent with a large amount of non-solvent, and even if the polyvinylidene fluoride resin can not be melted at room temperature, it can melt at a high temperature. Therefore, the concentration of the polyvinylidene fluoride resin in the dope solution for producing the hollow fiber membrane can be increased.

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

This is for further illustrating the present invention, and the scope of the present invention is not limited to these examples.

≪ Example 1 >

A dope solution prepared by mixing 40% by weight of polyvinylidene fluoride, 10% by weight of dimethylacetamide and 50% by weight of benzene dicarboxylic acid alkyl ester at 150 DEG C was transferred to a spraying nozzle for forming a support layer [ + Cost price) = 0.16].

10% by weight of polyvinylidene fluoride, 45% by weight of dimethylacetamide and 35% by weight of benzene dicarboxylic acid alkyl ester, 5% by weight of polyethylene glycol 1,000 and 5% by weight of polyvinylpyrrolidone 40,000, Was prepared and transferred to the injection nozzle for forming a pore layer.

A mixed solution consisting of 40% by weight of dimethylacetamide and 60% by weight of benzene dicarboxylic acid alkyl ester was transferred to the hollow transfer nozzle while maintaining the temperature at -10 ° C for the formation of the inner hole. And immersed in water as an external coagulation bath to solidify after spinning.

To remove the solvent contained in the prepared hollow fiber membrane, the membrane was immersed in isopropanol to completely remove the solvent, and then immersed in a final 40 wt% glycerin aqueous solution and dried to prepare a hollow fiber membrane. The hollow fiber separator had an outer diameter of 1.3 mm, an inner diameter of 0.7 mm, a pore size of 150,000 Da, and a permeability of 900 L / m 2 hr at 1 kgf / cm 2. The tensile strength (Load) was 0.9 MPa, the strain was 30%, and the peeling pressure was 12 bar.

<Example 2>

A hollow fiber membrane was prepared in the same manner as in Example 1 except that the external coagulating bath for solidifying after spinning was immersed in place of isopropanol in place of water. As a result of measuring the cross section of the hollow fiber membrane prepared above, it was confirmed that the hollow fiber membrane had a sponge-like cross-sectional structure without macro voids. The hollow fiber membrane thus prepared had an outer diameter of 1.6 mm and an inner diameter of 0.6 mm, a pore size of 100,000 Da, and a water permeability of 700 L / m 2 hr at 1 kgf / cm 2. The tensile strength was 0.7 MPa, the elongation was 40%, and the peeling pressure was 7 bar.

<Example 3>

In the preparation of the dope solution for forming the support layer, a mixed solution prepared by mixing 35% by weight of polyvinylidene fluoride, 10% by weight of dimethylacetamide and 55% by weight of benzene dicarboxylic acid alkyl ester at 150 ° C [ Solvent + non-solvent) = 0.15] was used in place of the solvent used in Example 1, to prepare a hollow fiber membrane. The prepared hollow fiber membrane had an outer diameter of 1.33 mm, an inner diameter of 0.75 mm, a pore size of 200,000 Da, and a permeability of 1100 L / m 2 hr at 1 kgf / cm 2. The tensile strength was 0.8 MPa, the elongation was 40% and the peeling pressure was 9 bar.

<Example 4>

In the preparation of the dope solution for forming the support layer, a mixed solution prepared by mixing 45% by weight of polyvinylidene fluoride, 5% by weight of dimethylacetamide and 50% by weight of benzene dicarboxylic acid alkyl ester at 150 ° C [ Solvent + non-solvent) = 0.09] was used in place of the solvent used in Example 1, to prepare a hollow fiber membrane. The prepared hollow fiber membrane had an outer diameter of 1.28 mm, an inner diameter of 0.67 mm, a pore size of 100,000 Da, and a permeability of 600 L / m 2 hr at 1 kgf / cm 2. The tensile strength was 1.0 MPa, the elongation was 20%, and the peeling pressure was 13 bar.

<Example 5>

In the preparation of the dope solution for forming the support layer, a mixed solution prepared by mixing 50% by weight of polyvinylidene fluoride, 5% by weight of dimethylacetamide and 45% by weight of benzene dicarboxylic acid alkyl ester at 150 ° C [ Solvent = non-solvent) = 0.1] was used in place of the solvent used in Example 1, to prepare a hollow fiber membrane. The prepared hollow fiber membrane had an outer diameter of 1.4 mm, an inner diameter of 0.7 mm, a pore size of 100,000 Da, and a permeability of 400 L / m 2 hr at 1 kgf / cm 2. The tensile strength was 1.3 MPa, the elongation was 20%, and the peeling pressure was 15 bar.

<Example 6>

A hollow fiber membrane was prepared in the same manner as in Example 1 except that the mixed solution was prepared and sprayed at 220 ° C instead of 150 ° C in the preparation of the dope solution for forming the support layer. The prepared hollow fiber membrane had an outer diameter of 1.18 mm, an inner diameter of 0.55 mm, a pore size of 400,000 Da, and a permeability of 1200 L / m 2 hr at 1 kgf / cm 2. The tensile strength was 0.7 MPa, the elongation was 50%, and the peeling pressure was 8 bar.

&Lt; Example 7 >

A hollow fiber membrane was prepared in the same manner as in Example 1 except that a mixed solution was prepared by mixing at 150 ° C instead of 100 ° C in the preparation of the dope solution for forming the pore layer. The cross-sectional structure of the hollow fiber membrane thus prepared was changed from a sponge structure to a macrovoid structure. The hollow fiber membrane thus prepared had an outer diameter of 1.21 mm, an inner diameter of 0.63 mm, a pore size of 500,000 Da, and a water permeability of 800 L / m 2 hr at 1 kgf / cm 2. The tensile strength was 0.8 MPa, the elongation was 40%, and the peeling pressure was 8 bar.

&Lt; Example 8 >

The procedure of Example 1 was repeated except that 30% by weight of non-volatile dimethylacetamide and 70% by weight of benzene dicarboxylic acid alkyl ester were used for the formation of the inner hole, Silica membranes were prepared. The prepared hollow fiber membrane had an outer diameter of 1.35 mm, an inner diameter of 0.74 mm, a pore size of a fraction molecular weight of 150,000 Da, and a permeability of 800 L / m 2 hr at 1 kgf / cm 2. The tensile strength was 1.1 MPa, the elongation was 20%, and the peeling pressure was 12 bar.

&Lt; Example 9 >

The procedure of Example 1 was repeated except that 60% by weight of non-volatile dimethylacetamide and 40% by weight of benzene dicarboxylic acid alkyl ester were used for the formation of the inner hole, Silica membranes were prepared. The hollow fiber membrane thus obtained had an outer diameter of 1.27 mm, an inner diameter of 0.69 mm, a pore size of 300,000 Da, and a water permeability of 1000 L / m 2 hr at 1 kgf / cm 2. The tensile strength was 0.7 MPa, the elongation was 40%, and the peeling pressure was 10 bar.

&Lt; Comparative Example 1 &

In the preparation of the dope solution for forming the support layer, a mixed solution prepared by mixing 48 wt% of polyvinylidene fluoride, 12 wt% of dimethylacetamide and 40 wt% of benzene dicarboxylic acid alkyl ester at 150 캜 was prepared [ (Solvent + non-solvent) = 0.23], a hollow fiber membrane was prepared in the same manner as in Example 1. The solution viscosity of the hollow fiber separator was excessively increased and the spinning was impossible.

Comparative Example 2

The procedure of Example 1 was repeated except that the content of the benzene dicarboxylic acid alkyl ester was changed to 20 wt% in the preparation of the dope solution for forming the porous layer of Example 1, A separator was prepared. The cross section of the hollow fiber membrane prepared above was measured, and macrovoids accounted for more than 50%. The hollow fiber membrane thus prepared had an outer diameter of 1.2 mm, an inner diameter of 0.7 mm, a pore size of 500,000 Da, and a capacity of 1200 L / m 2 hr at a water permeability of 1 kgf / cm 2. The tensile strength was 0.8 MPa, the elongation was 50%, and the peeling pressure was 8 bar.

&Lt; Comparative Example 3 &

In preparing the dope solution for forming the support layer, a mixed solution obtained by mixing 65% by weight of polyvinylidene fluoride, 3% by weight of dimethylacetamide and 32% by weight of benzenedicarboxylic acid alkyl ester at 150 ° C. [good solvent / (good solvent + Non-solvent) = 0.08], except that the hollow fiber membrane was prepared in the same manner as in Example 1. The prepared hollow fiber membrane was too viscous to be spinnable.

&Lt; Comparative Example 4 &

A hollow fiber membrane was prepared in the same manner as in Example 1 except that a mixed solution was prepared and sprayed at 100 ° C instead of 150 ° C in the preparation of the dope solution for forming the support layer. The hollow fiber separator produced gelation of the dope solution and was not spinnable.

&Lt; Comparative Example 5 &

A hollow fiber membrane was prepared in the same manner as in Example 1 except that, in the preparation of the dope solution for forming the pore layer, a mixed solution was prepared and sprayed at 10 ° C instead of 100 ° C. The hollow fiber separator produced was gelled during spinning and was not spinnable.

&Lt; Comparative Example 6 >

Except that a mixed solution obtained by mixing 40% by weight of polyvinylidene fluoride, 30% by weight of? -Caprolactone and 30% by weight of benzene dicarboxylic acid alkyl ester at 150 占 폚 was used in the preparation of the dope solution for forming the support layer Was prepared in the same manner as in Example 1 to prepare a hollow fiber membrane. The hollow fiber membrane thus obtained had an outer diameter of 1.28 mm, an inner diameter of 0.71 mm, a pore size of 200,000 Da, and a permeability of 1100 L / m 2 hr at 1 kgf / cm 2. The tensile strength was 0.5 MPa, the elongation was 10%, and the peeling pressure was 8 bar. Thus, the tensile strength and elongation of the hollow fiber separator prepared in the above-described example were much reduced compared to the hollow fiber separator prepared in Example 1. [

&Lt; Comparative Example 7 &

In the preparation of the dope solution for forming the support layer, a mixed solution obtained by mixing 40 wt% of polyvinylidene fluoride, 30 wt% of? -Butyrolactone, and 30 wt% of benzene dicarboxylic acid alkyl ester at 150 ° C , A hollow fiber membrane was produced in the same manner as in Example 1, The hollow fiber membrane thus prepared had an outer diameter of 1.32 mm, an inner diameter of 0.75 mm, a pore size of cut molecular weight of 300,000 Da, and a permeability of 800 L / m 2 hr at 1 kgf / cm 2. The tensile strength was 0.6 MPa, the elongation was 9% and the peeling pressure was 9 bar. Thus, the tensile strength and elongation of the hollow fiber separator prepared in the above-described example were much reduced compared to the hollow fiber separator prepared in Example 1. [

&Lt; Comparative Example 8 >

Except that a mixed solution obtained by mixing 40 wt% of polyvinylidene fluoride, 30 wt% of cyclohexanone, and 30 wt% of benzene dicarboxylic acid alkyl ester at 150 캜 was used in the preparation of the dope solution for forming the support layer Was prepared in the same manner as in Example 1 to prepare a hollow fiber membrane. The hollow fiber membrane thus prepared had an outer diameter of 1.40 mm, an inner diameter of 0.76 mm, a pore size of a fraction molecular weight of 150,000 Da, and a permeability of 700 L / m 2 hr at 1 kgf / cm 2. The tensile strength was 0.48 MPa, the elongation was 10%, and the peeling pressure was 8 bar. Thus, the tensile strength and elongation of the hollow fiber separator prepared in the above-described example were much reduced compared to the hollow fiber separator prepared in Example 1. [

&Lt; Comparative Example 9 &

In the preparation of the dope solution for forming the support layer, a mixture of 40 wt% of polyvinylidene fluoride, 5 wt% of dimethylacetamide, 25 wt% of? -Caprolactone and 30 wt% of benzene dicarboxylic acid alkyl ester at 150 ° C The hollow fiber membrane was prepared in the same manner as in Example 1, except that a solution was used. The hollow fiber membrane thus prepared had an outer diameter of 1.33 mm, an inner diameter of 0.72 mm, a pore size of a fraction molecular weight of 150,000 Da, and a permeability of 900 L / m 2 hr at 1 kgf / cm 2. The tensile strength was 0.54 MPa, the elongation was 10%, and the peeling pressure was 9 bar. Thus, the tensile strength and elongation of the hollow fiber separator prepared in the above-described example were much reduced compared to the hollow fiber separator prepared in Example 1. [

&Lt; Comparative Example 10 &

The same procedure as in Example 1 was carried out except that the pore layer transport path was changed to 1/2 of the support layer transport path in the injection nozzle of Example 1 above. In this case, gelation occurred during spinning and spinning was impossible.

&Lt; Comparative Example 11 &

The same procedure as in Example 1 was performed except that the pore layer transport path was changed to 1/11 of the support layer transport path in the injection nozzle of Example 1 above. In this case, gelation occurred during spinning and spinning was impossible.

Experimental Example 1 Observation of Cross Section Structure of Membrane

The cross-sectional structure of the hollow fiber membrane prepared in Example 1 was observed using a scanning electron microscope.

As a result, FIG. 1 shows the entire cross-section of the hollow fiber membrane produced in Example 1, FIG. 2 is a cross-sectional side view of the hollow fiber membrane produced in Example 1, Of the cross section.

Experimental Example 2 Evaluation of Properties of Membrane

The performance of the membrane was evaluated for the hollow fiber membranes prepared in the above Examples and Comparative Examples.

The pore size of the membrane was measured by measuring the fraction molecular weight. That is, the molecular weight was expressed as the fraction molecular weight when 90% or more of the polyethylene glycol was passed through an aqueous solution of 500 ppm of polyethylene glycol having different molecular weights.

The permeation amount of the membrane was measured by measuring the amount of permeation while flowing water from the outside of the membrane at a pressure of 1 kgf / cm 2 and a flow rate of 1 L / min at a temperature of 20 ° C.

The tensile strength (MPa) and elongation (%) of the film were measured by using a tensile tester at a speed of 50 mm / min until the 50 mm sample was broken.

As described above, the present invention provides a hollow fiber membrane having a two-layered cross-sectional structure in which a sponge-like outer pore layer and an inner support layer are combined without macrovoids.

The present invention optimizes the conditions of the solvent and the spray nozzle when forming the outer pore layer and the inner support layer to form the outer pore layer into a complete sponge-free form without macrovoids, thereby achieving a high rejection rate, But also has high porosity and high water permeability.

Further, by forming the inner supporting layer by increasing the concentration of the polyvinylidene fluoride resin using a mixed solvent in which the mixing ratio between the good solvent and the non-solvent benzene dicarboxylic acid alkyl ester is optimized, a high performance hollow fiber separator having excellent mechanical properties can be obtained Can be manufactured.

Accordingly, the high performance hollow fiber membrane according to the present invention is capable of removing pathogenic microorganisms and viruses while maintaining high water permeability, and has high strength due to the continuous connection of the polymers. Furthermore, the high performance hollow fiber membrane according to the present invention can be used for seawater desalination pretreatment, And in the field of concentration and purification.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.

Claims (18)

Sponge-shaped outer pore layer without macrovoids and
Polyvinylidene fluoride, 30 to 60% by weight and the inner formed by a good solvent and a benzene dicarboxylic acid C ₁ dope for forming a supporting layer made of a poor solvent is 40 to 70% by weight of the mixed-solvent cost ~C ₁₂ alkyl ester solution As the support layer is bonded structure,
The poor solvent is composed of a good solvent and a non-solvent of benzenedicarboxylic acid C _{1 to} C ₁₂ alkyl ester, but is mixed at a weight ratio of the following (1) to have a high exclusion rate and water permeability Hollow fiber membrane composed of polyvinylidene fluoride resin having excellent physical properties.
Positive solvent / (positive solvent + non-solvent) ≤ 0.2 (1) The hollow fiber membrane according to claim 1, wherein the outer pore layer is 5 to 100 µm thick. The hollow fiber membrane of claim 1, wherein the outer pore layer has a pore size of 0.01 to 0.08 μm. The hollow fiber membrane according to claim 1, wherein the inner support layer is 100 to 600 µm thick. The method of claim 1, wherein the permeate flow rate is measured while increasing the pressure by introducing distilled water at 20 ° C. into the hollow from the hollow fiber membrane, and the separation pressure at which the permeate flow rate rises is 8 to 15 bar. The hollow fiber membrane. The hollow fiber separator according to claim 1, wherein the hollow fiber separator has a tensile strength of 0.4 to 2.0 MPa and an elongation of 5 to 120%. The hollow fiber membrane of claim 1, wherein the hollow fiber membrane has a water permeability of 400 to 1200 L / m 2 hr under 1 kgf / cm 2 condition.


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