KR101806186B1 - Manufacturing method of ion exchange electrode, Ion exchange electrode, and Filter using ion exchange electrode - Google Patents

Abstract

The present invention relates to the production of an ion exchange electrode by the adhesion of an ion exchange sheet inserted between a roller and a roller. Specifically, the present invention relates to a method for manufacturing an ion exchange electrode, which comprises the following steps: a sheet manufacturing step for manufacturing a cation exchange sheet and an anion exchange sheet, respectively; an ion film adhesion step for adhering a cation membrane and an anion membrane on one side of the cation exchange sheet and the anion exchange sheet; an inserting step for inserting the cation exchange sheet and the anion exchange sheet into two rollers so that the cation membrane and the anion membrane are located on both sides of a catalyst layer; and a pressurizing step for pressurizing the cation exchange sheet and the anion exchange sheet, wherein the method increases the productivity through continuous production.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ion exchange electrode manufacturing method, an ion exchange electrode,

The present invention relates to a method of manufacturing an ion exchange electrode by adhering an ion exchange sheet inserted between a roller and a roller, an ion exchange electrode manufactured by an ion exchange electrode manufacturing method, and a filter using the ion exchange electrode.

Patent Document 001 relates to a waterproof sheet of a polymer (PP, PE, PVC, etc.) adhered between two rollers, wherein the waterproof sheet comprises a base material sheet; A pressure-sensitive adhesive layer of a solventless type applied on one side of the base material sheet; And a release paper adhered to the pressure-sensitive adhesive layer, wherein the pressure-sensitive adhesive layer is formed by forming a pressureless adhesive type pressure-sensitive adhesive layer made by mixing rubber, tackifier, heat stabilizer, antioxidant, reinforcing agent, .

Patent Document 002 discloses a method for producing a slurry, comprising the steps of: a) mixing an engineering plastic having an ion exchange functional group, an electrode active material and an organic solvent to prepare a slurry; b) applying the slurry to a current collector; And c) drying the current collector coated with the slurry. A negative electrode having a current collector coated with an engineering plastic having a cation exchanger, a slurry obtained by mixing an electrode active material and an organic solvent; A positive electrode having a current collector coated with an engineering plastic having an anion exchanger, a slurry obtained by mixing an electrode active material and an organic solvent; Or the cathode electrode and the anode electrode; The present invention relates to a system for desalinization.

It has advantages of high adsorption and desorption efficiency of ions in the process of operation and a simple manufacturing process of stable electrode in water without crosslinking reaction while increasing the adsorption capacity of the electrode.

Patent Literature 003 relates to a method for producing an ion exchange membrane integrated electrode of an electrodeposition desalination apparatus for removing ions in brine, comprising the steps of: pulverizing an ion exchange resin to form a powder; dissolving the ion exchange resin powder in a solvent Forming a slurry on the surface of the electrode; and spinning the slurry on the surface of the electrode by electrospinning to coat the electrode.

Patent Document 004 relates to an adhesive sheet for manufacturing a ferrite sheet composite, and more particularly to a first release film; A thermal adhesive layer provided on the first release film; An acrylic adhesive layer provided on the thermal adhesive layer; And the second release film provided on the acryl pressure-sensitive adhesive layer, it is possible to provide a pressure-sensitive adhesive sheet which does not require a separate protective substrate for protecting the ferrite sheet, and is easy to align when bonded to the ferrite sheet, The present invention also relates to an adhesive sheet for producing a ferrite sheet composite, which enables a sheet composite to be produced, including functional additives.

KR 10-0952689 B1 (Registered on April 06, 2010) KR 10-1029090 B1 (Registration date April 06, 2011) KR 10-2013-0068950 A (released June 26, 2013) KR 10-1510301 B1 (Registered on April 02, 2015)

The present invention relates to a method of manufacturing an ion exchange electrode by adhering an ion exchange sheet inserted between a roller and a roller, an ion exchange electrode manufactured by an ion exchange electrode manufacturing method, and a filter using the ion exchange electrode.

In order to solve the problems of the prior art, the method for producing an ion exchange electrode according to the present invention comprises: a sheet production step (S110) of producing a cation exchange sheet (110) and an anion exchange sheet (210) An ion-exchange membrane attaching step (S120) for attaching the cation membrane 120 and the anion membrane 220 to one surface of the anion exchange sheet; a cation exchange membrane and an anion exchange sheet attached so that the cation membrane and the anion membrane are positioned on both sides of the catalyst layer 310 And a sheet attaching step (S130).

The method for producing an ion exchange electrode of the present invention includes a step S210 of producing a cation exchange sheet 110 and an anion exchange sheet 210 respectively; a step of forming a cation film 120 or an anion film 220 A step of manufacturing a membrane (S220) for producing a bipolar membrane (400) by bonding the bipolar membrane, the cationic sheet and the anion sheet (S230).

In the method of manufacturing an ion exchange electrode according to the present invention, in the above-described methods, the step of attaching the sheets (S130, S230) includes inserting (S501) into two rollers (510, 520) (S502). ≪ / RTI >

In the method of manufacturing an ion exchange electrode according to the present invention, the membrane manufacturing step of the above-described method includes an anion membrane forming step (S221) of forming a thin film with an anion solution solution, a catalyst layer forming step (S222); and a cationic membrane producing step (S223) of forming a thin film with the cation solution solution after the catalyst layer producing step.

In the method of manufacturing an ion exchange electrode according to the present invention, the sheet manufacturing step (S110, S210) includes one selected from an extrusion step, a calendering step, and a fiber manufacturing step.

The ion exchange electrode of the present invention includes an ion exchange electrode manufactured by the above-described method.

The ion exchange filter of the present invention includes a case 800 formed with a charging hole 811 at one side thereof and a discharge hole 821 formed at the other side thereof and a housing space formed therein, And the electrode (100) in which the ion exchange electrode is received in a rolled or laminated form.

The present invention relates to a method for producing an ion exchange electrode, in which an ion exchange sheet and an ion membrane are preliminarily manufactured, and then two ion exchange sheets are bonded by a roller, thereby enabling automation and mass production.

The ion exchange electrode of the present invention permits the contact surface by the difference in the width of the sheet and the membrane, and additionally allows the contact surface by the space, so that the two sheet adhesion is easy.

The ion exchange electrode of the present invention transfers the ion exchange sheet to the two rollers, and the two ion exchange sheets are bonded by the pressure of the roller, and the flow path groove can be formed on the sheet surface at the same time as bonding.

The roller for manufacturing an ion exchange electrode according to the present invention forms a feeding protrusion on the surface of the roller, thereby precisely controlling the feeding speed of the sheet and preventing slippage between the sheet and the roller.

The sheet for ion exchange electrode of the present invention can be easily applied to an extrusion method, a calendering method, and a fiber production method.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view showing a cation exchange sheet and anion exchange sheet
Fig. 2 is a cross-sectional view of the ion-
Fig. 3 is a perspective view of the ion-exchange sheet combined with the roller pressing according to the present invention
4 is a view showing a process of manufacturing the membrane of the present invention
5 is a view showing a process for producing an ion exchange sheet according to the present invention
FIG. 6 is a perspective view of a filter utilizing an ion exchange electrode of the present invention

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.

(Example 1-1) A method for producing an ion exchange electrode according to the present invention comprises a sheet manufacturing step (S110) of producing a cation exchange sheet (110) and an anion exchange sheet (210), respectively; A step of attaching a cation membrane 120 and an anion membrane 220 on one side of the catalyst layer 310; a step of attaching a cation exchange membrane and an anion exchange membrane such that the anion membrane is positioned on both sides of the catalyst layer 310; Step S130.

Example 1-1 is a method of manufacturing an ion exchange electrode by contacting a cation exchange membrane having a cation membrane and an anion exchange sheet having anion membrane attached thereto. Specifically, a cation membrane is attached to the surface of the cation exchange sheet, and at the same time, an anion membrane is attached to the surface of the anion exchange sheet. Each of the ion-exchange sheets to which the cationic membrane and the anion membrane are attached is attached on the surface where the cationic membrane and the anionic membrane are formed. A catalyst layer is also formed between the cation membrane and the anion membrane.

(Example 1-2) In the ion-exchange electrode manufacturing method of the present invention, the width (B2) of the cation membrane and the anion membrane in the ion-membrane-adhering step in Example 1-1 is the same as that of the cation-exchange sheet and the anion- B1).

When an ion membrane is formed on the entire surface of the ion exchange sheet, adhesion of the ion exchange sheet is not smooth. That is, in order to form a contact surface on the ion exchange sheet, the ion membrane width is formed smaller than the width of the ion exchange sheet. Therefore, the corrugated portion where no ion membrane is formed forms a contact portion, thereby enabling the contact of two ion exchange sheets.

(Example 1-3) The ion exchange electrode manufacturing method of the present invention is characterized in that in Embodiment 1-2, the cation membrane and the anion membrane are formed at regular intervals, and a space S1 having a constant size is formed between each ion membrane do.

For smooth adhesion of the ion exchange sheet, the ion membrane is formed on the surface of the ion exchange sheet with a certain length, and an adhesion space is formed between the ion membranes. The adhesive space is utilized as a space for adhesion between the ion exchange sheets.

(Example 2-1) A method for producing an ion exchange electrode according to the present invention comprises a sheet production step (S210) of producing a cation exchange sheet (110) and an anion exchange sheet (210), respectively; A step S230 of manufacturing a bipolar membrane 400 by combining the bipolar membrane, the cationic sheet 120 and the anion membrane 220 to form a bipolar membrane 400; do.

Example 2-1 is a method of manufacturing an ion exchange electrode by bonding a cation sheet and an anion sheet to both sides of a bipolar membrane completed in advance. The bipolar membrane forms a cationic membrane on one side of the catalyst layer and an anion membrane on the other side of the catalyst layer. That is, the three layers are formed into a single structure. A cation sheet and an anion sheet are attached to both sides of the bipolar membrane, and the cation sheet is attached to the side where the cation membrane is formed, and the anion sheet is attached to the side where the anion membrane is formed.

(Example 2-2) In the method for producing an ion-exchange electrode of the present invention, the cation-exchange sheet and the anion-exchange sheet are continuously produced at a constant width in Example 2-1, the bipolar membrane is formed to have a constant length, The width is formed smaller than the width of the ion exchange sheet.

A bipolar membrane is inserted between two ion exchange sheets, and an ion exchange sheet is attached. In order to smoothly adhere the ion exchange sheet, the width of the bipolar membrane is formed to be smaller than the width of the ion exchange sheet so that both sides of the ion exchange sheet can be adhered. In addition, the bipolar membranes are formed in plural in the same length, and are continuously supplied and coupled with a certain space between the ion exchange sheets. That is, it is possible to secure a position at which the two ion exchange sheets can be contacted by the space.

(Example 3-1) In the ion-exchange electrode manufacturing method of the present invention, in the embodiment 1-1 or the embodiment 2-1, the sheet attaching step S130 or S230 is inserted into the two rollers 510 and 520 (S501); and a squeezing step (S502) which is squeezed by the roller.

Two rollers are rotated, a cation sheet and an anion sheet are inserted between the rollers, and the cation sheet and the anion sheet are conveyed and attached by roller rotation and squeezing. In Example 1-1, only the cation sheet and the anion sheet were transferred, while in Example 2-1, the bipolar membrane was inserted between the cation sheet and the anion sheet. The roller generates heat of 80 to 120 캜, and attaches the cation exchange sheet and the anion exchange sheet by heat. The temperature range is a numerical range in which an ion exchange sheet of a polymer material can be attached, and has a critical meaning for achieving an effective binding force. In another embodiment, the roller oscillates ultrasonic waves together with heat to couple the cation sheet and the anion sheet by ultrasonic vibration.

(Example 3-2) A method for producing an ion-exchange electrode of the present invention is the same as the method for producing an ion-exchange electrode according to the embodiment 3-1, except that the channel groove 601 is formed on the roller contact surface of the cation-exchange sheet and the anion- And a flow path forming step 240 for forming a flow path.

The roller surface forms a projection. The cation exchange sheet and the anion exchange sheet which are in contact with the roller surface are continuously formed by the protrusions, and the grooves are utilized as the flow path of the ion exchange electrode. That is, the roller forms a flow channel at the same time as the cation exchange sheet and the anion exchange sheet are attached.

(Example 3-3) The ion exchange electrode manufacturing method of the present invention is the same as the example 3-1 except that the ion exchange electrode manufacturing method according to the embodiment 3-1 is carried out by the ion exchange sheet 604 formed on the surface of the roller, .

The contact position of the cation exchange sheet and the anion exchange sheet should be accurate. If the sheet slips on the roller surface during the ion exchange sheet transfer process, it will cause a contact position error. In order to prevent this, a plurality of feeding projections are formed on the roller circumferential surface at uniform intervals on the roller surface. That is, the feeding protrusion forcibly feeds the ion exchange sheet during the rotation of the rollers, so that slipping can be prevented. Therefore, the contact positions of the cation exchange sheet and the anion exchange sheet can be precisely matched.

(Example 4-1) The method for producing an ion-exchange electrode of the present invention is the same as the method for producing an ion-exchange electrode according to the embodiment 2-1, wherein the membrane preparation step comprises: an anion membrane production step (S221) of forming a thin film with an anion solution solution; (S222) a catalyst layer forming step (S222) for forming a catalyst layer, and a cationic membrane forming step (S223) for forming a thin film with a cation solution solution after the catalyst layer forming step.

The bipolar membrane forms a catalyst layer between the cationic membrane and the anionic membrane. In the bipolar membrane manufacturing process, anion solution solution is cast on the release film surface and dried to form an anion film with a small thickness. The catalyst is uniformly dispersed on top of the dried anion membrane and dried to form a catalyst layer. The cation solution solution is dispersed on the dried catalyst layer and dried to form a cation membrane. Accordingly, a bipolar membrane formed in the order of lamination of an anion membrane, a catalyst layer, and a cation membrane can be manufactured on the mold release film surface, and then the bipolar membrane can be secured by removing the mold film.

(Example 4-2) The method for producing an ion exchange electrode of the present invention is the same as the method for producing an ion exchange electrode according to Example 4-1, wherein the step of forming the anion membrane comprises the step (221a) of applying an anion solution solution for applying an anion solution solution onto a release film surface; And a first drying step (221b) for drying the applied solution after the anion solution solution application step.

The anion solution solution contains a quaternary ammonium salt (-NH ₃ ), a primary to tertiary amine (-NH ₂ , -NHR, -NR ₂ ), a quaternary phosphonium group (-PR ₄ ), a tertiary sulfonium group ₃ ), which is an ion exchanger, is dissolved in a solvent and is capable of exchanging negative ions.

The polymer ionomer having an anion exchanger may be dissolved in an organic solvent and may be present as a solution. Examples of the polymer ionomer include polystyrene, polysulfone, polyisocyanurate, polyamide, polyphenylene oxide, polyester, polyimide, polyether, polyethylene, polytetra Fluoroethylene and polyglycidyl methacrylate may be used, or a polymer capable of having an anion exchanger of the same condition may be used.

The organic solvent may be selected according to the kind of the polymer ionomer having an anion exchange group. Examples of the solvent in which the polymer ionomer is dissolved include dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone acetone, chloroform, dichloromethane , Trichlorethylene, ethanol, methanol, n-hexane, or mixtures of two or more thereof. In addition, equivalent substances can be used as substitutes.

The solids content of the anion solution solution is preferably 1 to 30% by weight, more preferably 3 to 10% by weight. If the solid content is less than 1% by weight, the concentration of the ion exchange solution is too low and the solvent evaporation time is long and the film thickness is too thin. If the solid content is more than 30% by weight, the concentration of the ion exchange solution is too high, It has a disadvantage in that it has poor thickness control and smoothness and water decomposition efficiency is low.

The anion solution solution preferably has a water content of 5 to 70%, more preferably 10 to 50%, after drying the film. When the moisture content is less than 5%, the membrane resistance is high and the water decomposition efficiency is low. When the water content is 70% or more, the durability in water is inferior.

When the anion solution solution is cast on a release film to produce an anion exchange membrane, the thickness of the coating layer of the anion solution solution may be 0.1 to 200 mu m, preferably 5 to 30 mu m. When the thickness is less than 0.1 탆, the film resistance is low but the selectivity is low and the efficiency is low. When the thickness is more than 200 탆, the selectivity is good, but the membrane resistance is increased and the water decomposition efficiency is low.

The anion solution solution can be formed into a bipolar membrane having excellent water decomposition efficiency by maintaining a certain membrane without being dissolved by a solution containing a catalyst or a cation exchange solution after drying, and when it is dissolved, a homogeneous membrane can not be formed The water decomposition efficiency is lowered.

The modified film is a hydrophobic polymer film that is not thermally deformed at a drying temperature and can be easily separated after formation of a bipolar membrane.

(Example 4-3) The method for producing an ion exchange electrode of the present invention is the same as the method for producing an ion exchange electrode according to the embodiment 4-2, wherein the catalyst layer producing step comprises a catalyst solution applying step (S221c) of applying a catalyst solution to the surface of the first ion exchange membrane And a catalyst solution drying step (S221d) for drying the applied catalyst solution after the catalyst solution applying step.

The catalyst layer forming step is a step of forming a catalyst layer by coating a water decomposition catalyst on the anion film layer, and the catalyst layer is a material capable of accelerating water decomposition and not soluble in water.

The catalyst layer is formed by coating and drying a catalyst slurry in which metal hydroxide nanoparticles are dispersed in a solvent. The metal hydroxide is preferably used for nano-particle oxide of withdrawal (FeOH _3, FeOH ₂₎ or chromium hydroxide (CeOH _3), it is possible to this uniform material substitution. The dispersion solvent for the catalyst particles is preferably a dispersion solvent which is not dissolved in the anion membrane.

The coating method is spraying, dip coating, knife casting, doctor blade, spin coating, etc. The coating amount of the catalyst is 0.01 to 100 mg per unit area (cm ² ), but it is preferably 10 to 50 mg. When the amount of the catalyst is less than 0.01 mg, the decomposition voltage of the water rapidly increases. When the amount of the catalyst is more than 100 mg, the interfacial adhesion between the anion membrane and the cation membrane deteriorates and the water decomposition efficiency decreases.

(Example 4-4) In the method for producing an ion-exchange electrode of the present invention, in the embodiment 4-3, the cationic membrane producing step includes a cation solution applying step (S221e) for applying a cation solution solution to the surface of the catalyst layer (S221e) And a second drying step (S221f) for drying the applied solution after the application step.

The cationic solution is a solution of a sulfonic acid group (-SO ₃ H), carboxyl group (-COOH), phospho nikgi (-PO ₃ H _2), Phosphinicosuccinic nikgi (-HPO ₂ H), oh sonic group (-AsO ₃ H ₂ ) And a cellinonicking group (-SeO ₃ H), which are soluble in a solvent, are capable of exchanging cations.

The polymer ionomer having a cation-exchange group may be dissolved in an organic solvent and may be present as a solution. Examples of the polymer ionomer include polystyrene, polysulfone, polyisocyanurate, polyamide, polyphenylene oxide, polyester, polyimide, polyether, Fluoroethylene, and polyglycidyl methacrylate may be used. However, a polymer having a cation-exchange group may be used without limitation.

The organic solvent may be selected according to the type of the polymer ionomer having a cation exchanger. Examples of the solvent in which the polymeric ionomer is dissolved include dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone acetone, Any one or a mixture of two or more selected from chloroform, dichloromethane, trichlorethylene, ethanol, methanol and n-hexane can be used, and equivalent substances can be substituted.

In preparing the cationic solution, the solid content is preferably 1 to 30% by weight, more preferably 3 to 10% by weight. If the solid content is less than 1% by weight, the concentration of the cation solution solution is too low, and the evaporation time of the solvent is long and the thickness of the membrane is too thin. When the solid solution content is more than 30% by weight, It is difficult to control the thickness and the smoothness is poor and the water decomposition efficiency is low.

The cationic solution solution is preferably dried to a film and then preferably has a water content of 5 to 70%, more preferably 10 to 50%. When the moisture content is less than 5%, the membrane resistance is high and the water decomposition efficiency is low. When the water content is 70% or more, the durability in water is inferior.

When the cation solution solution is coated on the catalyst layer to form a cationic membrane, the coating layer thickness of the cation solution solution may be 0.1 to 200 탆, but is preferably 5 to 30 탆. When the thickness is less than 0.1 탆, the membrane resistance is low but the selectivity is low and the water decomposition efficiency is low. When the thickness is more than 200 탆, the selectivity is good, but the membrane resistance is increased and the water decomposition efficiency is low. In addition, when the composite membrane is manufactured, it is preferable to use the same anion exchange solution and cation exchange solution having the same water content to make the same thickness.

(Example 5-1) The ion-exchange electrode manufacturing method of the present invention is the same as the production method of Example 1-1 or Example 2-1 except that the sheet manufacturing step (S110, S210) is an extrusion step, a calendering step, Or the like.

(Example 5-2) A method for producing an ion-exchange electrode according to the present invention is characterized in that in the method for producing an ion-exchange electrode according to the embodiment 5-1, the extruding step is a mixing step (S011) of mixing an ion-exchange powder resin and a binder (S012) which, after the melting step, an extrusion step (S013) in which the sheet combination produces a sheet by means of an extrusion die.

In the cation exchange sheet and the anion exchange sheet, the anion resin powder and the cation exchange resin powder are melted and mixed with the binder, respectively, and then the mixture is extruded by an extruder to produce a sheet.

Cation-exchange resin powder is a sulfonic acid group (-SO ₃ H), carboxyl group (-COOH), phospho nikgi (-PO ₃ H _2), Phosphinicosuccinic nikgi (-HPO ₂ H), oh sonic group (-AsO ₃ H ₂ ) And a celinonick group (-SeO ₃ H), and the anion exchange resin powder is a quaternary ammonium salt (-NH ₃ ), a primary to tertiary amine (-NH ₂ , -NHR , An anion exchange resin having an anion exchange group such as -NR ₂ , a quaternary phosphonium group (-PR ₄ ) and a tertiary sulfonium group (-SR ₃ ) is used. A substance capable of exchanging a cation and an anion may be substituted.

The ion exchange resin powder preferably has an average particle diameter of 1 to 500 μm, more preferably 1 to 100 μm or less. If it is out of the above range, it is difficult to form a uniform ion exchange adsorbent sheet on the bipolar membrane, It may become difficult to form a coating layer on the substrate.

The binder may be any material that can be melted at a temperature below which the functional groups of the ion exchange resin powders such as LLDPE, LDPE, PE copolymer, PP, EVA, and EOR are not decomposed. Preferably, powdery LLDPE or EVA is suitable The average particle diameter of the powder is preferably 1 to 2,000 μm, more preferably 1 to 700 μm or less, but not limited thereto, and it is possible to use a thermoplastic polymer resin that can uniformly mix and bind with the ion exchange resin powder.

The content of the binder in the preparation of the mixture of the ion exchange resin powder and the binder is preferably 10 to 70% by weight, more preferably 30 to 50% by weight. When the content of the binder is less than 10 wt% or more than 70 wt%, the melt flowability is low, so that the melt compression sheet is difficult to manufacture or the polymer binder completely encapsulates the ion exchange resin powder or does not have porosity, The resistance of the ion may be lowered or the water decomposition efficiency may be lowered.

The kneading step of uniformly mixing the ion-exchange resin powder with the polymer binder to knead a kneaded mass is performed by kneading the ion-exchange resin powder and the thermoplastic polymer binder by using a pressure dispersion kneader, The kneading temperature and time may be varied depending on the kind of the polymer binder. If the temperature of the kneader is kneaded at room temperature for about 2 hours, the temperature of the kneader is set to be higher than the softening point of the polymer binder. If the temperature is too low, the viscosity of the polymer becomes higher and mixing becomes difficult. More preferably 20 ° C or more higher than the softening point. At this time, if the heating temperature is too high, a homogeneous mixture is not well formed due to the decomposition of the binder, and if it is too low, the mixing time becomes long.

The kneader is preferably a type having a stirring blade or a roll kneader, but is not limited thereto as long as it can be uniformly kneaded. The amount of the feedstock to be added to the kneading machine is preferably 10 vol% or more, more preferably 15 to 50 vol%, of the volume of the mixer. The kneading time is preferably from 5 minutes to 5 hours, and more preferably from 30 minutes to 120 minutes until the time to cause viscosity change. The obtained kneaded product is preferably provided as pellets in a predetermined size so as to be easy to handle, and the production method of the pellets is not limited as long as it can enter the hopper of the extruder and maintain a shape that can easily produce a product.

When the kneaded product of the ion exchange resin powder and the thermoplastic polymer binder is formed through the melt extrusion process, the temperature inside the extruder is determined depending on the type of the binder, but preferably the temperature is higher than the melting temperature of the binder, It is preferable to set the temperature at which the functional group of the powder is not decomposed.

(Example 5-3) The ion-exchange electrode manufacturing method of the present invention includes the peeling step (S014) of Example 5-2 in which the sheet surface is peeled off after the above-mentioned extrusion step.

The surface of the ion exchange sheet that has passed through the extrusion die has a problem that the resistance is increased because the structure becomes locally dense during the molding process. To solve this, the dense tissue is removed, which causes the surface to peel off by a sandblasting process.

(Example 5-4) The ion exchange electrode production method of the present invention is the same as the production method of Example 5-1, wherein the calendering production step is a kneading step (S021) of kneading an ion exchange powder resin and a binder, And a stretching step (S022) of stretching the mixed material after the step.

A polymer binder solution having a cation exchange resin or anion exchange resin is kneaded to prepare a polymer binder solution which can be produced in the form of a sheet and a kneading step in which a cation or anion exchange resin powder is added to the polymer solution and kneaded, The kneaded material is subjected to a stretching step to produce a sheet.

The polymer resin powder having a cation exchanger may be a polymer resin powder having a sulfonic acid group (-SO ₃ H), a carboxyl group (-COOH), a phosphonic group (-PO ₃ H ₂ ), a phosphonic group (-HPO ₂ H) ₃ H _2), cell Reno nikgi (-SeO ₃ H), and the polymer resin powder having a cation exchange group is a quaternary ammonium (-NH _3), 1 ~ ₃ primary amine _{(-NH 2, -NHR, -NR 2} ) , A quaternary phosphonium group (-PR ₄ ), and a tertiary sulfonium group (-SR ₃ ) are used.

The organic solvent in which the polymer resin is dissolved is selected from the group consisting of dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone acetone, chloroform, dichloromethane, trichloro , One or a mixture of two or more selected from ethylene, ethanol, methanol, n-hexane and aqueous solution is used.

In addition, the present invention can be used by adding a pore-forming material together with the above-described ion-exchange resin powder as needed, and any material capable of forming pores of the sheet can be used without limitation. Specifically, for example, a material capable of forming pores in a sheet such as salt, porous silica, or activated carbon can be used.

The kneading of the ion-exchange resin powder with the polymer binder solution to knead the kneaded material into kneaded mass is performed by kneading the kneaded materials by a pressurized dispersion kneader, The kneading temperature and the kneading time are determined. The raw materials such as the ion-exchange resin powder and the pore-forming material are first kneaded dry, then the binder solution is kneaded, and the ion-exchange resin powder mixture is impregnated with a liquid binder. At this time, the temperature of the kneader is raised to the kneading temperature, and the temperature is higher than the softening point of the temperature-raising binder. If the temperature is too low, the viscosity of the binder increases and mixing becomes difficult. It is good to do. If the heating temperature is too high, the kneading mass for the galvanizing process is not well formed by the decomposition of the binder, and if it is too low, the kneading time becomes longer. The kneader is preferably a type having a stirring blade or a roll kneader, but is not limited thereto as long as it can be kneaded uniformly. The amount of the feedstock to be added to the kneading machine is usually 10 vol% or more, preferably 15 to 50 vol%, relative to the volume of the mixer. The kneading time is from 5 minutes to 5 hours, preferably from 30 minutes to 120 minutes, until a time when a large viscosity change occurs. The obtained kneaded product may be used for calendering as it is, and it is preferable to provide the kneaded product in a predetermined size so as to be easily handled. The molding method is not particularly limited as long as the shape can be maintained.

(Example 5-5) The ion-exchange electrode manufacturing method of the present invention is similar to that of Example 5-1, except that the fiber manufacturing step includes a radical step (S031) of forming a radical by irradiating the polymer fiber with radiation, A graft reaction step (S032) in which a monomer is graft-reacted with a polymer fiber in a polymerization solution; and a sulfone step (S033) in which a polymer fiber is sulfonated after the grafting step.

The polymer fibers may be selected from the group consisting of polyethylene fibers, polypropylene fibers, polycarbonate fibers, polyphenylene ether fibers, polyethylene terephthalate fibers, polybutylene terephthalate fibers, polyvinyl chloride fibers, polymethylmethacrylate fibers and polyamide fibers Polymer fibers can be used.

The irradiation may be an ion beam, an electron beam, a gamma ray, an alpha ray and a beta ray. The irradiation dose is preferably from 10 kGy to 500 kGy, more preferably from 25 kGy to 200 kGy, and most preferably from 50 kGy to 150 kGy. However, when it is less than 10 kGy, there is a problem that grafting of monomers to polymer fibers is difficult because of insufficient irradiation dose and insufficient formation of radicals, and when it exceeds 500 kGy, polymer fibers are decomposed.

The polymerization solution is prepared by dissolving the polymer in a solvent such as ethanol, methanol, dimethylformamide, formaldehyde, chloroform, dimethylacetamide, pyridine, propanol, benzene Benzene, xylene, toluene, 1,4-dioxane, tetrahydrofuran and the like are used.

Monomers such as styrene, vinyl toluene, alpha methyl styrene, t-butyl styrene, chlorostyrene, vinyl naphthalene, isopropenyl naphthalene, acrylic acid and methacrylic acid are used. The graft reaction temperature is preferably from 30 캜 to 90 캜, and most preferably from 45 캜 to 75 캜. Also, the graft reaction time can be from 1 hour to 72 hours.

As the production cost increases due to the expensive solvent, a method of dropping the sulfonic acid group reagent and circulating the solvent using an acidic pump is used to minimize the amount of solvent consumed in the sulfonation reaction.

The sulfonation reaction means a reaction in which a SO3H group is introduced into an organic compound to synthesize a sulfonic acid. The step of sulfonating the polymer fibers grafted by the graft polymerization method after the irradiation of the radiation comprises preparing a solution necessary for the sulfonation reaction and immersing the grafted polymer fibers in the solution. Derivatives of the sulfonation reaction solution are aromatic compounds having a benzene ring and include derivatives such as styrene, benzene, phenol, benzoic acid, and nitrobenzene.

Reagents containing sulfonic acid groups include, but are not limited to, sulfuric acid, fuming sulfuric acid, sulfur trioxide, and chlorosulfuric acid, and the reaction solvent is ethanol, methanol, dimethylformamide, formaldehyde ), Chloroform, dimethylacetamide, pyridine, propanol, benzene, xylene, toluene, 1,4-dioxane, tetra A solvent such as tetrahydrofuran may be used.

The sulfonic acid reaction time is preferably from 1 hour to 10 hours. When the sulfonation reaction time is less than 1 hour, sufficient sulfonation reaction does not proceed. When the sulfonation reaction time exceeds 10 hours, the polymer fibers are carbonized.

The concentration of the sulfonic acid group-containing reagent is most preferably 1 wt% to 5 wt%. However, when the concentration of the reagent is less than 1 wt%, the SO 3 H is insufficient and the normal sulfonation reaction does not proceed. When the concentration exceeds 5 wt%, carbonization of the polymer fiber occurs.

The amination reaction means a reaction in which an -NR 3 group is introduced into an organic compound to synthesize quaternary ammonium. And a step of carrying out chloromethylation of the polymer fiber grafted by the graft polymerization method after the irradiation with the radiation and an amination reaction step. The derivative is an aromatic compound having a benzene ring and is a styrene, benzene, phenol, benzoic acid, nitro Benzene and the like.

The chloromethylation reaction was carried out in a 2 L reactor equipped with a stirrer, a nitrogen inlet, a temperature controller, and a reflux condenser, while slowly passing nitrogen gas through the reactor, grafted polymer fibers (20 g), paraformaldehyde (PFA) Was added to chloroform (CF) (660 ml), and reacted for 72 hours. Then, the reaction mixture was separated by precipitation into methanol, distilled water was added thereto, Washed several times and dried.

The dried chloromethylated polymer fibers were placed in 500 mL of dichloroethane, and then 100 g of tertiary amine, trimethylamine (TMA), and 100 g of N, N, N ', N'-tetramethylhexamethylenediamine (TMHDA) 33.3 g, and the mixture was subjected to amination reaction at 30 ° C for 48 hours, and washed with methanol to obtain aminated polymer fibers.

(Example 6-1) The ion-exchange electrode of the present invention is an ion-exchange electrode manufactured by the method of Example 3-1.

The ion exchange electrode of the present invention can be manufactured by the method of Example 3-1 as well as by all the methods shown in all the examples presented in this specification.

 (Example 7-1) The ion exchange filter of the present invention comprises a case 800 forming a charging hole 811 on one side, a discharge hole 821 on the other side and forming a receiving space therein, And an electrode (100) mounted in the accommodation space, the ion exchange electrode of Example 6-1 being received in a rolled or laminated form.

In the ion exchange filter, the electrodes manufactured by the ion exchange electrode fabrication method of the above-described embodiment are laminated in a roll form or in a plate form. The ion exchange electrode which is dried or photographed is accommodated in the case, and a charging hole is formed at one side of the case to supply the input water, and a discharge hole is formed at the other side to discharge the ion-exchanged input water. A DC current is energized in the case and current flows through the seat. The cation exchange sheet and the anion exchange sheet each contain cations and anions, and the cation membranes and the anion membranes can pass only respective ions, and can easily discharge the ion exchanged water.

100: electrode 110: cation exchange sheet
120: Cationic membrane 210: Anion exchange sheet
220: anion membrane 310: catalyst layer
400: bipolar membrane 510: roller
520: roller 601:
604: Feeding protrusion 800: Case
811: input hole 821: exhaust hole

Claims (7)

In the ion exchange electrode manufacturing method,
A sheet manufacturing step S110 for manufacturing the cation exchange sheet 110 and the anion exchange sheet 210, respectively;
(S120) of attaching a cation membrane (120) and an anion membrane (220) to one side of the cation exchange sheet and the anion exchange sheet;
A step S130 of attaching a cation exchange sheet and an anion exchange sheet so that the cation membrane and the anion membrane are positioned on both sides of the catalyst layer 310;
The sheet attaching step (S130, S230) is an inserting step (S501) of inserting into the two rollers (510, 520);
A squeezing step (S502) in which the sheet is squeezed using heat by the roller;
In the ion film deposition step, the width (B2) of the cation membrane and the anion membrane is formed to be smaller than the width (B1) of the cation exchange sheet and the anion exchange sheet, and the cation membrane and the anion membrane are formed at regular intervals, And forming a space (S1) having a predetermined size.
In the ion exchange electrode manufacturing method,
A sheet manufacturing step S210 for manufacturing the cation exchange sheet 110 and the anion exchange sheet 210, respectively;
A membrane fabrication step S220 of fabricating the bipolar membrane 400 by bonding the cation membrane 120 or the anion membrane 220 to both sides of the catalyst layer 310;
A step of attaching the bipolar membrane, the cation exchange sheet, and the anion exchange sheet (S230);
The sheet attaching step (S130, S230) is an inserting step (S501) of inserting into the two rollers (510, 520);
A squeezing step (S502) in which the sheet is squeezed using heat by the roller;
Wherein the cation exchange sheet and the anion exchange sheet are continuously produced at a constant width, the bipolar membrane is formed to have a constant length, and the bipolar membrane width is formed to be smaller than the width of the ion exchange sheet.
delete The method of claim 2,
The membrane manufacturing step may include an anion film forming step (S221) for forming a thin film with an anion solution solution;
A catalyst layer forming step (S222) for forming a catalyst layer after the anion-film forming step;
And (C223) a cationic membrane producing step (S223) of forming a thin film with the cation solution solution after the catalyst layer producing step.
The method according to claim 1 or 2,
The sheet manufacturing step (S110, S210) comprises producing the ion exchange electrode by any one of an extrusion step, a calendering step, and a fiber manufacturing step.
An ion exchange electrode produced by the method of claim 1 or 2.
A case 800 forming a charging hole 811 at one side and a discharge hole 821 at the other side and forming a receiving space therein;
And an electrode (100) mounted in the accommodation space, the ion exchange electrode of claim 6 being received in a rolled or laminated form.

Images