KR20140056558A - Method for manufacturing hollow fiber membrane and high flux and high strength hollow fiber membrane manufactured therefrom - Google Patents

Method for manufacturing hollow fiber membrane and high flux and high strength hollow fiber membrane manufactured therefrom Download PDF

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Publication number
KR20140056558A
KR20140056558A KR1020120120640A KR20120120640A KR20140056558A KR 20140056558 A KR20140056558 A KR 20140056558A KR 1020120120640 A KR1020120120640 A KR 1020120120640A KR 20120120640 A KR20120120640 A KR 20120120640A KR 20140056558 A KR20140056558 A KR 20140056558A
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KR
South Korea
Prior art keywords
hollow fiber
fiber membrane
membrane
weight
parts
Prior art date
Application number
KR1020120120640A
Other languages
Korean (ko)
Inventor
김동성
임성한
최정은
권자영
Original Assignee
주식회사 효성
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Priority to KR1020120120640A priority Critical patent/KR20140056558A/en
Publication of KR20140056558A publication Critical patent/KR20140056558A/en

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    • 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
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • 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
    • 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
    • B01D71/06—Organic material
    • B01D71/30—Polyalkenyl halides
    • B01D71/32—Polyalkenyl halides containing fluorine atoms
    • B01D71/34—Polyvinylidene fluoride
    • 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
    • D01D1/02—Preparation of spinning solutions
    • 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
    • D01D5/24—Formation of filaments, threads, or the like with a hollow structure; Spinnerette packs therefor
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/08—Addition of substances to the spinning solution or to the melt for forming hollow filaments
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/20—Specific permeability or cut-off range
    • 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

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

Abstract

The present invention relates to a method for manufacturing a hollow fiber membrane and a high flux and high strength hollow fiber membrane manufactured by the same. The hollow fiber membrane is manufactured by the phase transition of a spinning solution including polyvinylidene difluoride and acetylation of methyl cellulose. The hollow fiber membrane manufactured according to the present invention has excellent water permeability and strength. Moreover, the hollow fiber membrane is highly pollution-resistant and thus maintains excellent performance even when used for a long period time.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a hollow fiber membrane, and a method for manufacturing the hollow fiber membrane,

The present invention relates to a method for producing a hollow fiber membrane, and a high-strength and high-strength hollow fiber membrane produced therefrom, and more particularly, to a spinning solution comprising polyvinylidene difluoride and acetylated methyl cellulose, The present invention relates to a method for producing a hollow fiber membrane excellent in permeability and strength, and a hollow fiber membrane produced therefrom.

The global environmental market is expected to be one of the largest markets with the expansion of the market in the future along with the energy market. Membrane is attracting much attention as next generation water treatment technology. The membrane water treatment business began to be applied on a commercial scale from the end of the 1990s, and has been growing with the increase of processing facilities and large-scale improvement in the 2000s. In recent years, the world-leading advanced companies have expanded their business, And / or merger, and is securing the economical and reliability of membrane water treatment facilities of tens of thousands of tons / day. Therefore, the existing chemical and physical treatment facilities are expected to be rapidly replaced in order to secure technological and economic competitiveness for large-scale water treatment plants of several hundred thousand tons / day within the next 10 years. In order to secure the reliability of large-scale water treatment facilities, it is necessary to secure high-permeability membranes that exceed the processing limit of existing materials.

On the other hand, polysulfone, polythylsulfone, polyacrylonitrile and the like were mainly used for the water treatment membrane material in the 1990s. In recent years, fluorine resin-based polymers such as polyethylene dichloride, which is advantageous in terms of chemical resistance and durability against chlorine-based chemicals used as washing chemicals, are widely used. However, all of these membrane materials are hydrophobic polymers and have been pointed out as a disadvantage of low permeability. Therefore, hydrophilic property is required for the hydrophilic property of the material, and development of the surface hydrophilization of the membrane is progressing. However, the hydrophilization technology of the hydrophobic polymer membrane causes additional process and cost, thereby deteriorating the price competitiveness of the membrane, it's difficult. Therefore, it is necessary to develop a new high-strength hydrophilic polymer membrane that overcomes the limitations of existing membrane materials.

It is an object of the present invention to provide a method for producing a hollow fiber membrane excellent in mechanical strength and water permeability by using a polyvinylidene fluoride polymer and a hydrophilic polymer acetylated methyl cellulose (AMC).

Another object of the present invention is to provide a polyvinylidene fluoride hollow fiber membrane excellent in mechanical strength and water permeability, including acetylated methylcellulose, which is a hydrophilic polymer.

According to an aspect of the present invention,

Stirring a solution containing 20 to 50 parts by weight of polyvinylidene difluoride, 50 to 70 parts by weight of an organic solvent and 1 to 10 parts by weight of acetylated methyl cellulose (AMC) to prepare a spinning solution;

Defoaming the spinning solution and passing it through a tubular spinneret having a double structure to produce a hollow fiber membrane;

Phase-transforming the produced membrane in an external coagulating solution to solidify it; And

And washing and drying the coagulated hollow fiber membrane.

Another aspect of the present invention relates to a high strength and high yield hollow fiber membrane comprising acetylated methyl cellulose produced by the above production method.

The hollow fiber separator according to the present invention is excellent in permeability compared to a separator made of a hydrophobic polymer by preparing a separator using acetylated methylcellulose, which is a hydrophilic material, with polyvinylidene difluoride. Therefore, since the amount of permeated water is large at the same membrane area, the module of the separation membrane is required to be less at the time of installing the water treatment facility, which is economically advantageous. Further, by using a hydrophilic material, it is also advantageous in stain resistance, which is a weak point of a hydrophobic material, and the operation stability is excellent even in long-term operation.

Hereinafter, each step constituting the method for producing a polymer membrane according to embodiments of the present invention will be described in detail.

 (1) spinning solution preparation step

In the present invention, the spinning solution is prepared by mixing 20 to 50 parts by weight of polyvinylidene difluoride and 1 to 10 parts by weight of acetylated methyl cellulose with 50 to 70 parts by weight of an organic solvent and stirring at 150 to 240 ° C for 2 to 6 hours . If the temperature is lower than 150 ° C, the solubility may be lowered. If the temperature is higher than 240 ° C, it is difficult to control the production process. If the content of polyvinylidene difluoride is less than 20 parts by weight, the flowability of the spinning solution increases, and there is a problem that macropores are present on the cross section and the physical properties of the separator membrane become weak. When the content of polyvinylidene difluoride is more than 50 parts by weight, .

Examples of usable solvents include N, N'-dimethylformamide, N-methyl-2-pyrrolidone, N, N'-dimethylacetamide N, N'-dimethylacetamide, dimethylsulfoxide, chloroform, tetrahydrofuran, dimethyl phthalide (DMP), diethyl phthalide (DEP), dibutyl phthalate (DBP) Dioctyl phthalate (DOP), gamma-butyrolactone, and the like, but the present invention is not limited thereto.

Further, in an embodiment of the present invention, a separate additive may be additionally used to control the pore size of the separator to be produced. This is referred to as a pore regulator, which is a well-known method in the art, and a known pore-controlling agent is selected and added in an appropriate amount to meet the desired pore size. Poly (ethylene glycol), poly (vinylpyrrolidone), and poly (vinyl alcohol) may be selectively used as a pore regulator for increasing the pore size, and pore regulators for reducing the pore size include 1,4 -Dioxane, diethylene glycol dimethyl ether, etc. may be optionally used.

(2) Coagulation step

The hollow fiber membrane was fabricated by using a tubular spinning nozzle with a double structure which can simultaneously discharge the solution after the defoaming process with the internal coagulant. The membrane was immersed in a coagulating solution composed of a non-solvent or a mixture of a non-solvent and a solvent, Coagulate the membrane. In an embodiment of the present invention, water, alcohol, etc. may be used as the non-solvent, but the present invention is not limited thereto.

 (3) Removal of residual solvent and drying step

And then treated with water at about 50 to 90 DEG C for 10 to 30 hours to remove the solvent remaining in the membrane produced through the solidification step. Thereafter, the membrane is dried to obtain a porous hollow fiber membrane.

The hollow fiber membrane produced by the above production method is excellent in strength and water permeability and excellent in stain resistance due to the use of a hydrophilic polymer and thus excellent in operation stability even in long-term operation.

Hereinafter, the structure and effects of the present invention will be described in more detail with reference to specific examples. However, these examples are merely for the purpose of understanding the present invention more clearly and do not limit the scope of the present invention.

Example  One :

30 parts by weight of polyvinylidene fluoride, 10 parts by weight of acetylated methyl cellulose and 10 parts by weight of polyvinyl pyrrolidone were mixed with 50 parts by weight of diethyl phthalide and stirred at 180 ° C for 6 hours to prepare a spinning solution. The prepared spinning solution was defoamed and cooled and discharged by using a tubular spinning nozzle having a double structure. The spinning solution was immersed in water at 4 ° C for solidification. The prepared separator was immersed in water at 25 DEG C for 6 hours to remove residual solvent and then dried. The results of the permeability and strength of the prepared membrane are summarized in Table 1 below.

Example  2 :

5 parts by weight of acetylated methylcellulose, and 35 parts by weight of polyvinylidene fluoride were used to prepare a hollow fiber membrane in the same manner as in Example 1. The results of the permeability and strength of the prepared membrane are summarized in Table 1 below.

Example  3:

7 parts by weight of acetylated methyl cellulose and 33 parts by weight of polyvinylidene fluoride were used to prepare a hollow fiber membrane in the same manner as in Example 1. The results of the permeability and strength of the prepared membrane are summarized in Table 1 below.

Comparative Example  One :

40 parts by weight of polyvinylidene fluoride was mixed with 60 parts by weight of diethyl phthalate and stirred at 180 DEG C for 6 hours to prepare a spinning solution. The prepared spinning solution was defoamed and cooled and discharged by using a tubular spinning nozzle having a double structure. The spinning solution was immersed in water at 4 ° C for solidification. The prepared separator was immersed in water at 25 DEG C for 6 hours to remove residual solvent and then dried. The results of the permeability and strength of the prepared membrane are summarized in Table 1 below.

[Pure water permeability of membrane]

A mini-module consisting of 7 strands with a length of 35 cm of the hollow fiber membrane was prepared. The distilled water was used as raw water and distilled water was flowed for 30 minutes under the conditions of 25 ° C. and 50 kPa of filtration pressure, and the water was transferred to the balance for 5 minutes to measure the water content (g). The pure water permeability was measured by converting the measured water amount (g) into the unit water amount (h), the effective membrane area (m 2 ), and the water permeability (LMH L / m 2 / h) at a pressure of 100 Kpa.

[Measurement of Strength of Membrane]

The tensile strength at break (kgf / cm 2 ) was determined using a tensile tester (Instron 5565-standard) with a chuck distance of 50 mm and a tensile speed of 200 mm / min. This strength was divided by the membrane area to determine the judgment strength (Mpa). The final strength was measured by measuring 10 samples and averaging them.

Example 1 Example 2 Example 3 Comparative Example 1 Permeability (LMH) 1,539 1,435 1,206 834 Strength (Mpa) 10.9 11.4 11.5 11.5

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit and scope of the invention as set forth in the appended claims. Modifications and variations are intended to be included within the scope of the present invention.

Claims (5)

Stirring a solution containing 20 to 50 parts by weight of polyvinylidene difluoride, 50 to 70 parts by weight of an organic solvent and 1 to 10 parts by weight of acetylated methyl cellulose (AMC) to prepare a spinning solution;
Defoaming the spinning solution and passing it through a tubular spinneret having a double structure to produce a hollow fiber membrane;
Phase-transforming the produced membrane in an external coagulating solution to solidify it; And
And washing and drying the coagulated hollow fiber membrane.
The method of claim 1, wherein the stirring is performed at 150 to 240 ° C for 2 to 6 hours.
The method of claim 1, wherein the organic solvent is selected from the group consisting of N, N'-dimethylformamide, N-methyl-2-pyrrolidone, N, N'-dimethylacetamide, dimethylsulfoxide, chloroform and tetrahydrofuran, (DMP), diethyl phthalide (DEP), dibutyl phthalide (DBP), dioctyl phthalide (DOP), gamma-butyrolactone Of the hollow fiber membrane.
The method of claim 1, wherein the spinning solution is one or more selected from the group consisting of poly (ethylene glycol), poly (vinylpyrrolidone), poly (vinyl alcohol), 1,4-dioxane, diethylene glycol dimethyl ether Wherein the porous separator further comprises a porosity regulator.
A high strength and high yield hollow fiber membrane prepared by the method of any one of claims 1 to 4.
KR1020120120640A 2012-10-29 2012-10-29 Method for manufacturing hollow fiber membrane and high flux and high strength hollow fiber membrane manufactured therefrom KR20140056558A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20180085715A1 (en) * 2016-09-27 2018-03-29 Lotte Chemical Corporation Composition for membrane, method of preparing membrane using the same, membrane prepared therefrom and apparatus for purifying water

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20180085715A1 (en) * 2016-09-27 2018-03-29 Lotte Chemical Corporation Composition for membrane, method of preparing membrane using the same, membrane prepared therefrom and apparatus for purifying water
CN107866153A (en) * 2016-09-27 2018-04-03 乐天化学株式会社 Film and water purification installation prepared by film composition, the method for preparing the film, the film composition

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