KR20200095238A - Heterogeneous membrane and its manufacturing method - Google Patents

Abstract

The present invention relates to a method of manufacturing a heterogeneous membrane used for desalination water treatment and a heterogeneous membrane manufactured by the method. Particularly, the present invention consists of a time series step including: a material generation step (S300) of mixing an ion exchange resin powder (100), an ion exchange solution (200), a polymer solute (300) and a solvent (400) to produce an ion exchange mixture (10) in the form of sludge; and a thin film forming step (S300) of forming a thin film (20) of the sludge after the material generating step. The heterogeneous membrane exhibits a function similar to that of a homogeneous membrane and thus has an effect of reducing production costs.

Description

Heterogeneous membrane and its manufacturing method}

The present invention relates to a method of manufacturing a heterogeneous membrane used for desalting water treatment and an invention of a heterogeneous membrane produced by the method.

Patent Invention 001 relates to a bipolar ion exchange membrane and a method of manufacturing the same, wherein a heterogeneous ion exchange membrane of a first polarity and a matrix having an ion exchange group of a second polarity made of an ion exchange resin powder and a binder resin having an ion exchange group of the first polarity A homogeneous ion exchange membrane of a second polarity made of resin is laminated, and the interface between the heterogeneous ion exchange membrane of the first polarity and the homogeneous ion exchange membrane of the second polarity presents a bipolar ion exchange membrane that is a heterogeneous interface.

Patent Invention 002 relates to an ion exchange membrane that is provided in an electric desalination device to remove or concentrate dissolved ions. 50 to 54 wt% of an ion exchange resin-40 to 50 wt% of a polymer complex-5 to 10 wt% of polyethylene glycol After charging at the content ratio, kneading for 20 to 40 minutes at a temperature range of 130 to 150°C to prepare a mixture, injecting the mixture into an extruder, extruding to a thickness of 0.5 to 2.0 mm, and forming into a flat sheet, It is characterized in that the sheet is immersed in a crosslinker to crosslink by immersing it for 1 to 3 hours at a temperature range of 80 to 100°C using pure water with an additive added at a content ratio of 3.0 to 5.0 wt%.

Patent Invention 003 relates to an ion exchange membrane used for the purpose of selective ion permeation in an electrochemical water purifying apparatus, and proposes manufacturing by mixing ionic resin powder and PTFE into an IPA solution. In particular, it is possible to manufacture at a low temperature of 50-60°C, and at the same time, it is possible to shorten the manufacturing time to less than 30 minutes, and it has hydrophilicity, which suggests excellent ion permeability.

Patent Invention 004 relates to an ion exchange membrane used in an electrodialysis device, and more specifically, to a surface modification of a heterogeneous ion exchange membrane using plasma to improve ion permeability by making the heterogeneous ion exchange membrane into a homogeneous ion membrane. In particular, the introduction of micropores on the surface of the film-forming composite of the heterogeneous ion exchange membrane increases the chance of ion permeation. In the case of oxygen plasma, carbonyl and hydrosyl groups are introduced, increasing the wettability of the membrane to water and ions dissolved in water. It increases the chance of permeation and presents a technology for treating acrylic acid plasma on a cation exchange membrane.

KR 10-2018-0109473 A (Publication date October 8, 2018) KR 10-0547592 B 1 (Registration date January 23, 2006) KR 20-2009-0003092 U (Publication date April 1, 2009) KR 10-1999-003661 A (Publication date January 15, 1999)

The present invention relates to a method of manufacturing a heterogeneous membrane used for desalting water treatment and an invention of a heterogeneous membrane produced by the method.

The present invention is an invention of a method for producing a heterogeneous membrane, and ion exchange resin powder (100), ion exchange solution (200), polymer solute (300) and solvent (400) are mixed to form a sludge-type ion exchange mixture (10). The material generation step (S300) of generating; After the material generation step, a thin film forming step (S300) of forming a thin film 20 from the sludge; consists of a time series procedure including.

The present invention is an invention of a method for producing a heterogeneous film, and in the procedure presented above, a drying step (S400) of drying the film after the thin film forming step is included.

The present invention is an invention of a method for producing a heterogeneous film, and in the procedure presented above, the polymer solute 300 is formed of a polyolefin resin 300a.

The present invention is an invention of a method for manufacturing a heterogeneous membrane, and in the procedure presented above, the material generation step (S300) comprises an ion exchange resin powder (100) in a solvent (400), ion exchange And a mixing step (S100a) of simultaneously mixing the solution 200 and the polyolefin-based resin 300a.

The present invention is an invention of a method for manufacturing a heterogeneous membrane, and in the above-described procedure, the first mixing step (S110b) of mixing the ion exchange solution 200 and the NMP (400a) in the material generation step (S300); A second mixing step (S120b) of dissolving the polyolefin resin (300a) in the NMP (400a); After the first mixing step and the second mixing step, a third mixing step (S130b) of mixing the product of the first mixing step and the ion exchange resin powder 100; After the third mixing step, a fourth mixing step (S140b) of mixing the material produced by the third mixing step and the material produced by the second mixing step; Includes.

The present invention is an invention for a heterogeneous membrane, and includes a heterogeneous membrane manufactured by any one of the above-described manufacturing methods.

Since the ion exchange resin powder, ion exchange solution, and PVDF of the present invention are mixed, they exhibit a function similar to that of a homogeneous membrane, thereby reducing production cost.

In the present invention, the membrane resistance, water content, ion exchange resistance, and thickness can be set according to the difference in content of ion exchange resin powder, ion exchange solution, and PVDF.

1 is a method for producing a heterogeneous film according to conditions of simultaneous mixing of a mixture
2 is a method for producing a heterogeneous film according to the stage mixing conditions of the mixture material

Hereinafter, the most preferred embodiment of the present invention will be described in detail in order to describe in detail that a person skilled in the art to which the present invention pertains can easily implement the present invention.

The numbers cited in the following examples are not limited to the citation targets, and may be applied to all examples. An object exhibiting the same purpose and effect as the configuration presented in the Examples corresponds to an equivalent substitution object. The higher concept presented in the examples includes lower concept objects that are not described.

[Example 1-1] The present invention relates to a method for manufacturing a heterogeneous membrane, and an ion exchange resin powder (100), an ion exchange solution (200), a polymer solute (300) and a solvent (400) are mixed to form a slurry (30). ) A substance generation step of generating an ion exchange mixture 10 in the form of (S300); After the material generating step, a thin film forming step (S300) of forming a thin film 20 of the slurry is performed in a time series procedure.

The present invention relates to a method for producing a heterogeneous membrane used for desalting water treatment. The heterogeneous membrane has the advantage of inexpensive production cost compared to the homogeneous membrane, but causes problems of low moisture content and high membrane resistance. In order to overcome this, the present invention may overcome the disadvantages of moisture content and membrane resistance by mixing a polymer solute (PVDF: a polyolefin resin such as Poly Vinylidene Fluoride) in addition to the ion exchange resin powder. In addition, it is possible to secure excellent mechanical properties of the membrane at the same time. Therefore, it has the effect of producing a high-quality film (equivalent to a homogeneous film) despite the low production cost.

[Example 1-2] The present invention relates to a method for manufacturing a heterogeneous film, and in Example 1-1, a filtering step (S400) of filtering the slurry after the material generation step is included.

In the filter step of the present invention, the ion exchange resin powder and polymer solute that are not completely dissolved are separated by using a mesh net 500. It is preferable that the size of the mesh network is 100 μm. This is to form a uniform thin film in the film forming step.

[Example 1-3] The present invention relates to a method of manufacturing a heterogeneous film, and in Example 1-1, the thin film forming step is prepared by a casting method.

In the casting process of the present invention, the thickness of the thin film is 500 μm to 800 μm, preferably 600 μm. The thickness of the thin film is to finally secure a film having a thickness of 150 μm by evaporation of the solvent in the drying process described later.

Regarding the reason and effect of the above value, if the thickness is less than 100 μm, the resistance of the ion barrier plate is low, but the selectivity is low, and the desalination efficiency may be lower. If the thickness is more than 500 μm, the selectivity is good, but the resistance of the ion exchange membrane increases, resulting in lower desalination efficiency. So the above figures are taken into account.

[Example 1-4] The present invention relates to a method for producing a heterogeneous film, and in Examples 1-3 or 1-4, the solvent is formed of an amphoteric solvent.

[Example 1-5] The present invention relates to a method for producing a heterogeneous film, and in Example 1-4, the solvent is formed of any one selected from NMP, DMF, DMAc, or DMSO.

Since the NMP, DMAc or DMAo has high hydrophobicity and water immersion, it has the effect of being easily dissolved with any polymer. Therefore, any solute can be completely melted and a homogeneous solution can be secured during the mixing process.

[Example 2-1] The present invention relates to a method for manufacturing a heterogeneous film, and in Example 1-1, after the thin film forming step, a drying step (S400) of drying the film;

[Example 2-2] The present invention relates to a method for manufacturing a heterogeneous film, and in Example 2-1, the drying step includes drying with an infrared lamp 600.

The drying step of the present invention is a step of removing the solvent (solvent) contained in the thin film. The drying step can be dried with hot air, but hot air drying causes a problem that the surface is dried first and the interior is not sufficiently dried. In addition, excessively high temperature may be generated by hot air drying, which may cause separation of functional groups. However, when the infrared lamp of the present invention is used, heat at a uniform temperature acts over the entire thin film, so that simultaneous drying effects can be obtained at an appropriate temperature.

[Example 3-1] The present invention relates to a method for producing a heterogeneous film, and in Example 1-1, the polymer solute 300 is formed of a polyolefin resin 300a.

[Example 3-2] The present invention relates to a method of manufacturing a heterogeneous membrane, and in Example 3-1, the ion exchange resin powder 100 is used as a cation resin powder 110 or an anion resin powder 120. Formed; includes.

The ion exchange resin powder of the present invention is formed of a polymer, has a functional group for exchanging cations or anions, and must be easily soluble in a solvent. Specifically, as an ionomer, polystyrene, polysulfone, polyisosulfone, polyamide, polyphenylene oxide, polyphenylene sulfide, polyester, polyimide, polyether, polyethylene, polytetrafluoroethylene and polyglycidyl methacryl Any one or a mixture of two or more selected from the group consisting of rates and the like may be used.

[Example 3-3] The present invention relates to a method for producing a heterogeneous membrane, and in Example 3-1, the polyolefin resin may be PP, PE, PS, ABC, PA, PVC, PET, etc., Preferably, it is formed of PVDF ((Poly Vinylidene Fluoride).

[Example 4-1] The present invention relates to a method for manufacturing a heterogeneous membrane, and in Example 3-1, the ion exchange mixture 10 in the material generation step (S300) is ion-exchanged with the solvent 400 And a mixing step (S100a) of simultaneously mixing the resin powder 100, the ion exchange solution 200, and the polyolefin resin 300a.

[Example 5-1] The present invention relates to a method for manufacturing a heterogeneous membrane, and in Example 3-1, in the material generation step (S300), the ion exchange solution 200 and the NMP (400a) are mixed. A first mixing step (S110b); A second mixing step (S120b) of dissolving the polyolefin resin (300a) in the NMP (400a); After the first mixing step and the second mixing step, a third mixing step (S130b) of mixing the product of the first mixing step and the ion exchange resin powder 100; After the third mixing step, a fourth mixing step (S140b) of mixing the material produced in the third mixing step and the material produced in the second mixing step (S140b).

[Example 5-2] The present invention relates to a method for producing a heterogeneous film, and in Example 4-1 or Example 4-2, 15 wt% of PVDF powder relative to 100 wt% of NMP in the second mixing step To mix; includes.

Ion exchange solution, ion exchange resin powder, and PVDF are mixed with a solvent (NMP) to create a slurry, but depending on the order of the mixing process, the mixture quality is affected, and also the physical properties and functions of the membrane are affected.

In order to obtain optimal mixing conditions and film production effects, the fourth step should be performed in a time series procedure. The ion exchange solution and the NMP solvent mixed at a certain ratio form a liquid primary material, and the polyolefin resin mixed at a certain ratio is dissolved in the NMP solvent to form a liquid secondary material, respectively. The primary material is mixed with the ion exchange resin powder at a constant ratio to form a tertiary material in a slurry state, and the tertiary material may be obtained by mixing the secondary material prepared above to obtain a finished quaternary material. Thus, the quaternary material forms a slurry form.

In the present invention, a heterogeneous membrane membrane is formed by mixing an ion exchange resin powder, an ion exchange solution, and a polymer resin powder. If the amount of ion exchange solution presented above is excessive, the membrane has disadvantages of brittleness and increased membrane resistance. In addition, it has the disadvantage of rapid moisture content change depending on the synthesis ratio of the ion exchange solution and PVDF. Therefore, it is possible to obtain the effect of reducing the film resistance and improving the moisture content according to an appropriate synthesis ratio.

[Example 6-1] The present invention relates to a heterogeneous membrane, and includes a heterogeneous membrane produced by the method of manufacturing a heterogeneous membrane of the example presented above.

The present invention is a product invention of a heterogeneous membrane, and is an invention of a product produced by a manufacturing method produced by the method of the above-described embodiment. Therefore, there is a specificity of the method procedure, and the time-series steps of the procedure affect the object.

10: ion exchange mixture 20: thin film
30: slurry 100: ion exchange resin powder
110: cation resin powder 120: anion resin powder
200: ion exchange solution 300: polymer solute
300a: polyolefin resin 400: solvent
400a: NMP 500: mesh net
600: infrared lamp

Claims (6)

In the method of manufacturing a heterogeneous film,
A material generation step (S300) of mixing the ion exchange resin powder (100), the ion exchange solution (200), the polymer solute (300) and the solvent (400) to produce an ion exchange mixture 10 in the form of a sludge;
After the material generating step, a thin film forming step (S300) of forming a thin film 20 from the sludge;
Heterogeneous film manufacturing method comprising a.
The method according to claim 1,
After the thin film forming step, a drying step (S400) of drying the film; a heterogeneous film manufacturing method comprising a.
The method according to claim 1,
The polymer solute 300 is formed of a polyolefin resin (300a);
Heterogeneous film manufacturing method comprising a.
The method according to claim 3,
In the material generation step (S300),
The ion exchange mixture 10 is a heterogeneous membrane comprising a mixing step (S100a) of simultaneously mixing the ion exchange resin powder 100, the ion exchange solution 200, and the polyolefin resin 300a in a solvent 400; Manufacturing method.
The method according to claim 3,
In the material generation step (S300),
A first mixing step (S110b) of mixing the ion exchange solution 200 and the NMP 400a;
A second mixing step (S120b) of dissolving the polyolefin resin (300a) in the NMP (400a);
After the first mixing step and the second mixing step, a third mixing step (S130b) of mixing the product of the first mixing step and the ion exchange resin powder 100;
After the third mixing step, a fourth mixing step (S140b) of mixing the material produced by the third mixing step and the material produced by the second mixing step;
Heterogeneous film manufacturing method comprising a.
In a heterogeneous membrane,
A heterogeneous membrane prepared according to any one of claims 1 to 6.

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