KR20160006154A - Method for composite membrane module - Google Patents

Abstract

A manufacturing method of a composite membrane module of the present invention comprises the steps of: manufacturing a single membrane module in which a hollow fiber support layer is potted; and forming an active layer by interfacial polymerization, which enables a first solution containing amine and a second solution containing acyl halide to be in contact with the surface of the hollow fiber support layer in order. The manufacturing method is capable of forming an active layer with uniform thickness, with excellent processability. The composite hollow fiber membrane module manufactured by the method has excellent exclusion ratio of salt.

Description

[0001] METHOD FOR COMPOSITE MEMBRANE MODULE [0002]

The present invention relates to a method of making a composite membrane module. More particularly, the present invention relates to a method of making a composite membrane module using a single membrane module with a hollow support layer.

Membrane technology has been applied to recent water treatment. For example, microfiltration (MF) membranes and ultrafiltration (UF) membranes are used for water treatment in water purification plants, and reverse osmosis membranes are used for desalination of seawater. Reverse osmosis membranes and nanofiltration membranes are also used for processing semiconductor water, boiler water, medical water, and laboratory pure water. Water treatment technologies using these membranes are attracting attention due to their excellent processing capacity compared to installation space and low processing cost.

In recent years, unlike existing membrane processes that produce water permeation by applying pressure such as microfiltration, ultrafiltration, reverse osmosis, and nanofiltration, the osmotic pressure difference between the membranes is used as a driving force to cause water permeation. A forward osmosis (FO) process has attracted attention as a new area of water treatment. This is because the osmotic pressure is used as a driving force in contrast to the conventional separation membrane process, which enables water treatment to be performed at a lower energy than the conventional process requiring pressurization.

Since the development of composite membranes with improved performance in the early 1980s, almost 90% of the reverse osmosis membrane market has been replaced by a polyamide composite membrane in a single membrane.

The polyamide composite membrane is a composite membrane comprising a porous support layer made of a polysulfone polymer resin and a polyamide active layer as a surface selective layer. The selective layer may be formed by a thin layer dispersion method, an immersion coating method, a vapor deposition method, A Langmuir-Blodgett method, an interfacial polymerization method, and the currently developed and commercialized reverse osmosis composite membrane is used as a method for producing a composite membrane by the interfacial polymerization method disclosed in U.S. Patent No. 4,277,344.

As described above, the composite membrane is generally composed of a support layer and an active layer formed on the support layer, and the composite membrane module is manufactured by first preparing a composite membrane and then potting the composite membrane on the header of the module. However, since the porous hollow fiber support layer of a hollow fiber type has a cylindrical shape, it is not easy to form the active layer by coating the surface of the support layer with a uniform thickness due to its structural characteristics, A large number of potted or multiple bundle supporting layers must be individually coated to form an active layer, resulting in poor processability.

It is an object of the present invention to provide a composite membrane module for positive osmosis and a method of manufacturing the same.

Another object of the present invention is to provide a method for manufacturing a composite membrane module having excellent processability.

It is still another object of the present invention to provide a method of manufacturing a composite membrane module in which the thickness of the active layer is uniformly formed.

It is still another object of the present invention to provide a composite membrane module having excellent salt rejection rate and a method for producing the same.

The above and other objects of the present invention can be achieved by the present invention described below.

One aspect of the present invention provides a method of manufacturing a single membrane module, the method comprising: fabricating a single membrane module to which a hollow support layer is potted; And forming an active layer by interfacial polymerization by sequentially contacting a first solution containing an amine and a second solution containing an acyl halide on the surface of the hollow support layer.

The single membrane module comprising: a plurality of hollow fiber support layers potted at both ends; And a housing receiving the plurality of potted hollow support layers.

Wherein the hollow support layer is formed by spinning a polymer solution containing a polysulfone resin, an organic solvent, and a pore-forming agent to form a hollow fiber; Exposing the hollow fibers to air to form external pores; Immersing the hollow fiber having the external pore therein in a non-solvent to form an internal pore; And coagulating the hollow fiber.

The polysulfone-based resin may include polysulfone, polyethersulfone, or a combination thereof.

The organic solvent may include at least one component selected from the group consisting of N, N-dimethylformamide, N-methyl-2-pyrrolidone, dimethylsulfoxide and dimethylacetamide.

Wherein the pore-forming agent is selected from the group consisting of one selected from the group consisting of 2-ethoxyethanol, propionic acid, acetic acid, T-amyl alcohol, 2-methoxyethanol, methanol, ethanol, butanol, isopropyl alcohol, polyethylene glycol, Or more.

The non-solvent may include one or more components selected from the group consisting of water, methanol, ethanol and isopropanol.

The hollow support layer has an inner diameter of 0.1 to 3.0 mm and a layer thickness of 10 to 500 탆.

The hollow support layer may be a porous ultrafiltration membrane having a pore size of 10 nm to 100 m.

The pore size of the active layer may be 0.001 to 0.0001 탆.

The first solution may include polyamines and water, and the polyamines may be contained in an amount of 0.1 to 15% by weight based on 100% by weight of the first solution.

The polyamines may include components selected from the group consisting of phenylenediamine, cyclohexanediamine, piperazine, and mixtures thereof.

The second solution includes a polyfunctional acyl halide and an organic solvent, and the polyfunctional acyl halide may be included in an amount of 0.01 to 5 wt% based on 100 wt% of the second solution.

Examples of the polyfunctional acyl halide include tri-mesyl chloride, isophthaloyl chloride, terephthaloyl chloride, 1,3,5-cyclohexanetricarbonyl chloride, 1,2,3,4-cyclohexanetetracarbonyl chloride, And mixtures thereof.

The composite membrane module may be a pressurized module.

Another aspect of the present invention is to provide a composite membrane module manufactured by the above manufacturing method.

The salt rejection rate of the composite membrane module may be from 90 to 99.9%.

The method for producing a composite membrane module of the present invention can uniformly form the thickness of the active layer, is excellent in processability, and has an excellent salt rejection rate in a composite membrane module manufactured by the above method.

1 illustrates a cross-sectional view of a composite membrane module in accordance with an embodiment of the present invention.
FIG. 2 is a cross-sectional view of a composite membrane according to one embodiment of the present invention, wherein (a) is a cross-sectional view of a composite membrane including an active layer formed on an inner peripheral surface of a hollow support layer, Fig. 2 is a cross-sectional view of a composite membrane including

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, the techniques disclosed in the present application are not limited to the embodiments described herein but may be embodied in other forms. It should be understood, however, that the embodiments disclosed herein are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. In the drawings, the width, thickness, and the like of the components are enlarged in order to clearly illustrate the components of each device. In addition, although only a part of the components is shown for convenience of explanation, those skilled in the art can easily grasp the rest of the components. It is to be understood that when an element is described above as being located above or below another element, it is to be understood that the element may be directly on or under another element, It means that it can be done. 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. In the drawings, the same reference numerals denote substantially the same elements.

A method of manufacturing a composite membrane module of the present invention is a method of manufacturing a module including a composite membrane including a hollow support layer and an active layer formed on a surface of the support layer, ; Interfacially polymerizing a first solution containing an amine and a second solution containing an acyl halide in succession on the surface of the hollow support layer; And forming an active layer on the surface of the hollow support layer by the interfacial polymerization. In the detailed description of the present invention, the manufacturing method will be described separately for the production of a single membrane module and the manufacture of a composite membrane module using the single membrane module.

Single membrane  The manufacturing steps of the module

In the present invention, the single membrane module means a membrane module in which the active layer is not formed on the surface of the hollow fiber support layer.

Referring to FIG. 1, a single membrane module 100 according to one embodiment of the present invention includes a plurality of hollow support layers 20 having both ends potted; And a housing 10 for receiving the plurality of potted hollow support layers.

The single membrane module shown in Fig. 1 is a module in which water is collected at both ends of the module as a pressurized membrane module, and a raw water inlet 11 is formed at a lower end of one side of the housing 10, Process water outlets 12 and 13 are formed at the upper and lower ends of the housing, and a plurality of hollow fiber support layers 20 are potted in the housing in the longitudinal direction of the housing. In addition, not only the pressure-type module of the both-end collecting type but also the separating membrane module, the pressure-resistant type or the external pressure type pressure-type module which are collected at one end of the module may be used in the present invention. Depending on the type of the pressure- The number of the process water outlet ports, and the like can be designed and modified by a known method. The single membrane module used in the present invention may be an immersion membrane module in addition to the pressurized membrane module, but a pressurized module is preferable in terms of ease of coating.

The hollow support layer can be prepared by a Nonsolvent induced phase preparation process (NIPS). In one embodiment, the method for preparing a hollow support layer includes spinning a polymer solution containing a polysulfone resin, an organic solvent, and a pore-forming agent to form a hollow fiber; Exposing the hollow fibers to air to form external pores; Immersing the hollow fiber having the outer surface pores in a non-solvent to form an inner pore; And coagulating the hollow fiber. The outer pores are pores formed on the outer circumferential surface of the hollow fiber, and the inner pores are pores formed on the inner surface of the hollow fiber.

The polysulfone-based resin may include polysulfone, polyethersulfone, or a combination thereof, and may be contained in an amount of 10 to 20% by weight based on the total weight of the spinning solution.

The organic solvent may include at least one component selected from the group consisting of N, N-dimethylformamide, N-methyl-2-pyrrolidone, dimethylsulfoxide and dimethylacetamide.

The organic solvent may be contained in an amount of 60 to 89% by weight based on the total weight of the spinning solution.

Wherein the pore-forming agent is selected from the group consisting of one selected from the group consisting of 2-ethoxyethanol, propionic acid, acetic acid, T-amyl alcohol, 2-methoxyethanol, methanol, ethanol, butanol, isopropyl alcohol, polyethylene glycol, Or more.

The pore-forming agent may be contained in an amount of 1 to 20% by weight based on the total weight of the spinning solution.

The non-solvent may include one or more components selected from the group consisting of water, methanol, ethanol and isopropanol.

The hollow support layer produced by the NIPS process can be variously modified in various spinning conditions to form various structures, particularly asymmetric structures, and various additives can be added to adjust the pore size. It has an easy advantage.

The prepared hollow support layer is an ultrafiltration membrane, and the size of the pores formed on the surface of the support layer may be 10 to 100 탆.

The thickness of the hollow support layer may be 10 to 500 탆, and the hollow support layer may have an inner diameter of 0.1 to 3.0 mm. A mechanical strength and a sufficient water permeability that are usable in the above range can be achieved. Preferably 50 to 200 mu m.

Composite membrane  The manufacturing steps of the module

The composite membrane module can be manufactured by forming the active layer on the surface of the hollow support layer potted inside the housing using the single membrane module manufactured as described above.

In one embodiment, a first solution containing an amine and a second solution containing an acyl halide are sequentially brought into contact with the surface of the hollow support layer potted in the single membrane module. When the first solution and the second solution are sequentially brought into contact with the surface of the hollow support layer as described above, interfacial polymerization is performed on the surface of the support layer, and the active layer can be formed on the surface of the support layer by the interfacial polymerization.

In order to facilitate the circulation of the first solution into the hollow fiber in the module, water or bubbles must be removed in advance in the hollow fiber. To this end, air (air air is preferably injected. In addition, it is preferable that air is injected into the hollow fiber before the second solution is contacted after circulating the first solution to remove the remaining first solution, thereby imparting surface smoothness to the inner surface of the hollow fiber prior to contacting the second solution .

In order to prevent the hollow fiber from drying, the hollow fiber is preliminarily mixed with an aqueous solution containing 10 to 50% by weight of glycerin before interfacial polymerization with the first solution and the second solution or before porting the hollow fiber into the module, For 1 to 24 hours.

After the single membrane module having the hollow support layer is prepared as described above and the first solution and the second solution are injected into the module to coat the surface of the support layer, the coating layer is uniformly coated on the surface of the plurality of hollow support layers And an active layer having a uniform thickness may be formed on the surface of the support layer after the solidification step.

The surface of the hollow support layer in which the first solution and the second solution form a coating film may be an inner circumferential surface or an outer circumferential surface of the hollow support layer.

2 (a) is a cross-sectional view of a composite membrane 30 having an active layer 23 formed on an inner peripheral surface of a hollow fiber support layer 20, The first solution and the second solution may be circulatively contacted for 1 to 60 minutes under a pressure of 10 atm and an air blowing condition to uniformly coat the inner circumferential surface of the hollow support layer. Preferably, the first solution and the second solution injected into the hollow support layer should be removed from the air bubble before injection.

2 (b) schematically shows a cross-section of a composite membrane 30 in which an active layer 23 is formed on the outer circumferential surface of a hollow fiber support layer 20, After the first and second solutions are injected, a turbulent flow is performed under a pressure of 0.1 to 10 atm to uniformly coat the outer circumferential surface of the porous hollow support layer. Preferably, the first solution and the second solution injected into the hollow support layer should be removed from the air bubble before injection.

The active layer formed on the support layer may include a polyamide-based resin. By including the polyamide resin in this manner, a high salt rejection rate can be secured as compared with the conventional single membrane made of cellulose triacetate having a low salt rejection ratio.

In an embodiment, the active layer containing the polyamide may be formed by interfacial polymerization of the first solution and the second solution on the surface of the support layer containing the polysulfone-based polymer.

Specifically, a hydrophilic polysulfone-based hollow fiber support layer is contacted with a first solution containing an amine, and then a polysulfone-based hollow fiber support layer containing the first solution is contacted with a second solution containing a polyfunctional acyl halide To form an active layer containing polyamide on the surface of the support layer.

The first solution comprises a polyamine and water. Examples of the polyamine include phenylene diamine, cyclohexanediamine, piperazine, and the like, but are not limited thereto. The polyamine may be contained in an amount of 0.1 to 15% by weight based on the total weight of the first solution. The first solution may further include a polar solvent. The polar solvent may be an ethylene glycol derivative, a propylene glycol derivative, a 1,3-propanediol derivative, a sulfoxide derivative, a sulfone derivative, a nitrile derivative, a ketone derivative or a urea derivative.

The second solution comprises a polyfunctional acyl halide and an organic solvent. Examples of the polyfunctional acyl halide include trimesoyl chloride, isophthaloyl chloride, terephthaloyl chloride, 1,3,5-cyclohexanetricarbonyl chloride, 1,2,3,4-cyclohexanetetracarbonyl chloride and the like Can be used. These may be used alone or in combination of two or more. The double trimethoyl chloride is most preferable in terms of the salt removal ratio. The polyfunctional acyl halide may be used in an amount of 0.01 to 5% by weight based on the total weight of the second solution. As the organic solvent, aliphatic hydrocarbons having 5 to 12 carbon atoms may be used.

The coating time of each step of the interfacial polymerization may be 10 seconds to 20 minutes. It has the advantage of being uniformly coated in the above range, and when it is out of the above range, the thickness may become thick.

The active layer formed by the interfacial polymerization may have a thickness of 0.01 to 2 탆. There is an advantage that the water rejection rate necessary for effective membrane separation is achieved within the above range, while the water permeability is not low. Preferably 0.05 to 0.5 mu m.

The active layer may have a symmetrical or asymmetric structure and a pore size of 0.001 to 0.0001 탆.

The composite membrane module manufactured by the above-described manufacturing method is preferably used as a pressure-push type membrane module. The composite membrane module is excellent in the salt rejection rate because the thickness of the active layer of the composite membrane potted in the housing is uniform. The salt rejection rate of the composite membrane module may be from 90 to 99.9%.

Hereinafter, the present invention will be described in more detail by way of examples, but these examples are for illustrative purposes only and should not be construed as limiting the present invention.

Example

The mixture was mixed with 16 to 20% by weight of polysulfone, 69 to 73% by weight of N-methyl-2-pyrrolidone (NMP) and 7 to 11% by weight of polyvinylpyrrolidone (PVP) , Defoaming and spinning to produce a hollow fiber support layer.

The outer diameter (OD) of the produced hollow support layer was 0.7 to 1.3 mm, the ID (ID) was 0.5 to 1.0 mm, and the thickness (T) was 0.1 to 0.15 mm.

After the hollow support layer was potted, the first solution (2% aqueous solution of m-phenylenediamine (MPD)) was injected into the hollow fiber support layer at a pressure of 1 atm and circulated for 10 minutes. After the first solution circulation contact, the second solution (0.1% of 1,3,5-benzenetricarbonyltrichloride (TMC) organic solution) was pressurized at 1 atm for 10 minutes, and the inner surface of the hollow support layer was coated, Respectively. The active layer of the composite membrane had a thickness of 0.2 to 0.3 mu m and a pore size of 0.001 to 0.0001 mu m.

The salt rejection rate of the composite membrane was measured by the following method. The results are shown in Table 1 below. As a result, it was confirmed that the composite membrane according to the embodiment of the present invention is excellent in salt rejection rate.

Method of measuring exclusion rate

Two or three composite membranes prepared in the above examples were placed in a transparent acrylic tube having a diameter of 1 cm, and one end of the composite membrane and one end of the acrylic tube were sealed together with urethane, and the other end of the composite membrane was sealed. The module was prepared.

After preparing raw water having a raw water concentration C (feed) of 2000 ppm NaCl, the raw water was pressurized at 15 atm to the evaluation module and then the salt concentration C (permeation) of the treated water was measured. The exclusion rate was calculated according to the following equation.

Exclusion rate (%) = [1-C (permeation) / C (feed)] x 100

Flow rate (LMH) Exclusion rate (%) Example 25 to 30 95 to 97

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (17)

Fabricating a single membrane module having a hollow support layer potted thereon; And
A first solution containing an amine and a second solution containing an acyl halide are sequentially injected into the hollow support layer and an interface polymerization reaction is performed between the first solution and the second solution to form an active layer , ≪ / RTI >
Wherein the step of forming the active layer is carried out by circulating the first solution and the second solution under pressure and air blowing conditions of 0.1 to 10 atm.
2. The system of claim 1, wherein the single membrane module
A plurality of hollow fiber support layers potted at both ends; And
And a housing for receiving the plurality of potted hollow support layers.
The method of claim 1, wherein the hollow support layer
Spinning a polymer solution containing a polysulfone resin, an organic solvent and a pore-forming agent to form a hollow fiber;
Exposing the hollow fibers to air to form external pores;
Immersing the hollow fiber having the external pore therein in a non-solvent to form an internal pore; And
And coagulating the hollow fiber. ≪ RTI ID = 0.0 > 11. < / RTI >
4. The method of claim 3, wherein the polysulfone-based resin comprises polysulfone, polyethersulfone or a combination thereof.
4. The composite membrane module of claim 3, wherein the organic solvent comprises at least one component selected from the group consisting of N, N-dimethylformamide, N-methyl-2-pyrrolidone, dimethylsulfoxide and dimethylacetamide. ≪ / RTI >
4. The composition of claim 3, wherein the pore former is selected from the group consisting of 2-ethoxyethanol, propionic acid, acetic acid, T-amyl alcohol, 2-methoxyethanol, methanol, ethanol, butanol, isopropyl alcohol, polyethylene glycol and silica And at least one component selected from the group consisting of polypropylene and polypropylene.
4. The method of claim 3, wherein the non-solvent comprises at least one component selected from the group consisting of water, methanol, ethanol and isopropanol.
The method of claim 1, wherein the hollow support layer has an inner diameter of 0.1 to 3.0 mm and a layer thickness of 10 to 500 μm.
2. The method of claim 1, wherein the hollow support layer is a porous ultrafiltration membrane having a pore size of 10 nm to 100 m.
The method of claim 1, wherein the pore size of the active layer is 0.001 to 0.0001 m.
The method of claim 1, wherein the first solution comprises a polyamine and water, wherein the polyamine is present in an amount of 0.1 to 15 weight percent based on 100 weight percent of the first solution.
12. The method of claim 11, wherein the polyamine comprises a component selected from the group consisting of phenylenediamine, cyclohexanediamine, piperazine, and mixtures thereof.
The method of claim 1, wherein the second solution comprises a polyfunctional acyl halide and an organic solvent, wherein the polyfunctional acyl halide is included in an amount of 0.01 to 5 wt% based on 100 wt% A method of manufacturing a membrane module.
14. The method of claim 13, wherein the polyfunctional acyl halide is selected from the group consisting of trimesoyl chloride, isophthaloyl chloride, terephthaloyl chloride, 1,3,5-cyclohexanetricarbonyl chloride, 1,2,3,4-cyclo Hexane tetracarbonyl chloride, and mixtures thereof. ≪ RTI ID = 0.0 > 11. < / RTI >
The method of claim 1, wherein the composite membrane module is a pressurized type.
16. A composite membrane module produced by the method of any one of claims 1 to 15, wherein a polyamide active layer is formed on the inner circumferential surface of the hollow fiber support layer.
17. The method of claim 16,
Wherein the composite membrane module has a salt rejection rate of 90 to 99%.

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