KR20170017238A - Manufacturing method of desalination sheet and desalination sheet module - Google Patents

Abstract

The present invention relates to a method for manufacturing a desalination sheet for purified water and soft water of underground water, tap water, brackish water, heavy water, and industrial sewage, and to a desalination sheet module. The method for manufacturing an integral desalination sheet comprises: inputting a porous support capable of accumulating ions between a positive ion exchange membrane and a negative ion exchange membrane; and forming a flow path pattern around the positive ion exchange membrane and negative ion exchange membrane. The desalination sheet module can be operated by stacking the desalination sheets manufactured therefrom in layers, winding the same with a roll, and applying electric potential.

Description

Description: TECHNICAL FIELD The present invention relates to a desalination sheet and a desalination sheet module,

The present invention relates to groundwater, tap water, brackish water, purified water for industrial water and industrial wastewater, and a method for producing desalination sheet for soft water and a desalination sheet module. More particularly, the present invention relates to a method for producing an integral desalination sheet by sealing a periphery of a porous support capable of accumulating ions between a cation exchange membrane and an anion exchange membrane and forming a flow path pattern on the outer surface of the cation exchange membrane and the anion exchange membrane will be. Also, the present invention relates to a desalting sheet module capable of being operated by laminating a desalting sheet manufactured by the above method and winding it with a roll to apply a potential.

In the production of domestic water or industrial water, desalination technology plays a very important role in determining human health, process efficiency, and product performance.

Recently, researches on seawater desalination, wastewater and brine treatment methods due to water shortage have been actively conducted. Of these, ion exchange resins are widely used, but electrical separation processes have been researched to replace them due to the use of chemicals and economical problems in the regeneration of resins.

The capacitive deionization (CDI) process during the electrical separation process is based on the electric double layer theory of a capacitor, and the property that the relative polarity ions in the water quality are adsorbed on the electrode surface when electricity is applied to the electrode surface . That is, ions contained in the aqueous solution are removed by applying an electrostatic force when a solution containing a cation and an anion passes between the two porous carbon electrode layers. The CDI electrode is made by coating an electrode active material on a current collector of a conductive graphite foil which can directly apply electricity or by attaching a sheet to the electrode. These graphite current collectors are difficult to handle due to their low mechanical strength, It has a disadvantage that performance is deteriorated due to damage during assembly and a defect rate is high.

Electrodialysis and Electrodeionization using Cation Exchange Membrane and Anion Exchange Membrane should supply a separate electrolyte to the positive electrode and negative electrode and make a complicated flow path so that concentrated water and deionized water can flow separately, It is difficult to automate the process of assembling the modules and manual operation is required. Therefore, manufacturing cost is high.

Korean Patent No. 10-0763436 discloses a bipolar ion exchange membrane using a conductive mixture and a binder in the form of a powder and forming a cation exchange membrane and an anion exchange membrane. In this case, when the ion is adsorbed and regenerated, the adsorbed ions are desorbed by using the water decomposition reaction at the interface where the cation exchange membrane and the anion exchange membrane are attached. Therefore, it is necessary to use a high voltage and a drawback that the adsorption and desorption efficiency are low and heat is generated I have.

Therefore, it is necessary to develop the desalination technology which can newly improve the electrical separation process technique which has these disadvantages.

Korean Patent Registration No. 10-0763436

In order to solve the above-mentioned problems, the present invention provides a method for manufacturing an ion exchange membrane, comprising the steps of: placing a porous support capable of accumulating ions between a cation exchange membrane and an anion exchange membrane, sealing the edge, and forming a flow path pattern on the outer surface of the cation exchange membrane or the anion exchange membrane And a method for producing the integral desalinization sheet.

Since the present invention uses a cation exchange membrane and an anion exchange membrane in a porous support such as a woven fabric or nonwoven fabric having excellent mechanical strength without using a separate spacer to produce a desalted sheet, it is easy to handle, And to provide a method for producing a desalted sheet capable of reducing a defective rate and a defective rate.

Another object of the present invention is to provide a desalination sheet module which can be operated by laminating a desalting sheet and winding it with a roll so that the applied electric potential can be varied depending on the number of turns and the number of turns wound on the inside and outside of the roll.

The present invention is not limited to the conventional electrodialysis and electrodeionization modules, and it is difficult to have a plurality of channels or complicate the assembling process, and to make a large number of electrode terminals capable of providing electricity as in the storage desalination module And offers a desalination sheet module that is easy for commercial applications because it can make the same capacity design and size as existing commercial filter products.

The present invention relates to a process for producing a desalted sheet and a desalting sheet module comprising the desalted sheet produced therefrom.

The present invention relates to an ion exchange membrane, comprising: forming an ion exchange membrane using an ion exchange solution or an ion exchange resin powder; Attaching the ion exchange membrane to both sides of the porous support; And forming a channel patterning on the surface of the ion exchange membrane.

The ion exchange solution of the present invention may be one in which a polymer resin having a cation or anion exchanger is dissolved in an organic solvent to form an ion exchange membrane. The ion exchange resin powder may be a polymer resin having a powdery cation or anion exchanger, To form an ion exchange membrane.

The polymer resin of the present invention is selected from polystyrene, polysulfone, polyisocyanurate, polyamide, polyphenylene oxide, polyester, polyimide, polyether, polyethylene, polytetrafluoroethylene and polyglycidyl methacrylate , But is not limited thereto.

The porous support of the present invention may have any form selected from a polymer sheet, a thin film, a woven fabric, and a nonwoven fabric, but the present invention is not limited thereto.

The method of attaching the ion exchange membrane of the present invention to the porous support may be a method using an adhesive or a pressure sensitive adhesive, a method of curing an ion exchange solution, or a method using a binder mixture.

The present invention also relates to a desalting sheet module comprising the desalting sheet manufactured by the method for producing the desalting sheet.

The desalination sheet module of the present invention comprises: a desalting sheet comprising at least one desalting sheet; A porous tube in which the desalting sheet is wound in a cylindrical shape; A desalination sheet module case for allowing the desalination sheet to be installed therein; And a module cap sealing the module case; . ≪ / RTI >

In the desalination sheet module of the present invention, the desalination sheet may have a structure in which one or more layers are laminated, and the cation exchange membrane and the anion exchange membrane may be laminated in a manner facing each other and wound on the porous tube. The module case may be a positive electrode, And may further include an inlet and an outlet.

The desalted sheet manufactured according to the present invention can solve disadvantages such as complicated module assembling and work complexity which are difficult in the existing electrical desalination technique, and it is easy to handle desalted sheet because a porous support having excellent mechanical strength is used.

In addition, since the desalination sheet includes a channel pattern, it is not necessary to provide a separate spacer for providing a flow path when assembling the module, and it is possible to automate assembly of the module, thereby increasing the mass productivity.

It is possible to assemble various types of modules of a square shape and a cylindrical shape using the desalination sheet manufactured according to the present invention, minimize the volume, safely use it at a high water pressure, The module capacity and the operating voltage can be freely designed.

1 shows a structure of a desalination sheet according to this alias.
2 shows the adsorption regeneration operation of the desalination sheet module of the present invention.
FIG. 3 is a graph showing the results of desalination experiments according to Examples and Comparative Examples of the present invention.
4 to 7 show an exploded view and an assembled view of the desalination sheet module according to the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in more detail with reference to the accompanying drawings. It should be understood, however, that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the invention. In addition, unless otherwise defined, technical terms and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In the following description, The description of the known function and configuration will be omitted.

The present invention relates to a process for producing a desalted sheet and a desalting sheet module comprising the desalted sheet produced therefrom.

The desalting sheet manufacturing method of the present invention

Forming an ion exchange membrane using an ion exchange solution or an ion exchange resin powder; Attaching the ion exchange membrane to both sides of the porous support; And forming a channel pattern on the surface of the ion exchange membrane.

The ion exchange membrane according to the present invention includes a homogeneous or homogeneous membrane of a polymer resin having a cation or anion exchanger and the ion exchange solution includes a solution form in which a polymer resin having a cation or anion exchanger is dissolved in an organic solvent, The ion-exchange resin powder may be one in which a polymer resin having a cationic or anion-exchange group in powder form is mixed with a binder.

Examples of the polymer resin having an ion exchange group include a sulfonic acid group (-SO ₃ H), a carboxyl group (-COOH), a phosphonic group (-PO ₃ H ₂ ), a phosphonic group (-HPO ₂ H) (-AsO ₃ H _2), cell Reno nikgi (-SeO ₃ H) a polymeric resin or 1 to tertiary amine salt having a cation exchange group such as _{(-NH 2, -NHR, -NR 2} ), 4 ammonium salt (- NH ₃ ), a quaternary phosphonium group (-PR ₄ ), and a tertiary sulfonium group (-SR ₃ ), but the present invention is not limited thereto.

More specifically, the polymer resin having the ion exchanger may be selected from the group consisting of polystyrene, polysulfone, polyisocyanurate, polyamide, polyphenylene oxide, polyester, polyimide, polyether, polyethylene, polytetrafluoroethylene, But it is not limited thereto.

The weight average molecular weight of the polymer resin having the ion exchanger is not limited in order to achieve the object of the present invention, but is preferably 50,000 to 2,000,000. When the polymer resin having the above range is used, the viscosity of the electrode slurry and the electrode active material It has excellent characteristics.

The organic solvent may be selected according to the kind of the polymer resin. For example, the organic solvent in which the polymer resin is dissolved includes dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone acetone, chloroform, The solvent may be any one or a mixture of two or more selected from dichloromethane, trichlorethylene, ethanol, methanol and n-hexane, but is not limited thereto and may include all organic solvents capable of dissolving the polymer resin.

There is no limitation on the solid content in the polymer solution, but it is preferable that 1 to 30 wt% of 100 wt% of the total polymer solution is easy to coat on the porous support.

The ion-exchange resin powder preferably has an average particle diameter of 0.1 to 500 μm, more preferably 1 to 30 μm, and the ion exchange resin has an excellent ion exchange effect within the above range, but is not limited thereto.

In the mixture of the ion-exchange resin powder and the binder, the binder is a polymer material having a low glass transition temperature and stable at room temperature and water, and is uniformly mixed with the ion-exchange resin powder and can form a coating layer. Polymer materials can be used. Specifically, any one or a mixture of two or more selected from linear low density polyethylene (LLDPE), low density polyethylene (LDPE), polyethylene (PE), ethylene vinyl acetate (EVA), polyolefin, polyamide, polyester and polyurethane But is not limited thereto.

The composition of the mixture is preferably 40 to 60% by weight of the ion exchange resin powder and 60 to 40% by weight of the binder. But the present invention is not limited thereto.

The kneading step of uniformly mixing the ion-exchange resin powder with the binder to knead the kneaded mass is kneaded by using a pressure dispersion kneader. After kneading at room temperature for about 2 hours, the temperature of the kneader is kneaded It is preferable to set the temperature higher than the softening point of the ion exchange resin powder at a temperature higher than 10 ° C, but the present invention is not limited thereto.

The kneader is preferably a type having a stirring blade or a roll kneader, but is not limited 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, more preferably from 30 to 120 minutes until the time when the viscosity changes. The obtained mixture can be extrusion-melt-coated as it is, and it is preferable that the mixture is cut into a predetermined size so as to be easily handled, and the molding method is not limited as long as the shape is maintained.

The melt viscosity of the binder used in the present invention can be appropriately selected. However, it is preferably in the range of 10 to 7000 Pa · s, more preferably 200 to 5000 Pa · s at a temperature of 120 ° C. and a shear rate of 100 sec ^-1 to be. When the melt viscosity is in this range, the polyolefin in the present invention is excellent in coating property and adhesion.

The melt strength of the ion-exchange resin powder and the binder mixture used in the present invention can be appropriately selected, but preferably has a melt strength of 0.5 to 20 cN as measured under conditions of a shear rate of 100 sec ^-1 and a melt viscosity of 1400 Pa · s, 1 to 10 cN. When the melt strength is in the above range, an ion exchange membrane can be stably obtained particularly when a film is formed by the melt extrusion method.

The method for manufacturing a desalting sheet according to the present invention may include attaching ion exchange membranes of different polarities to both sides of a porous support.

The porous support of the present invention is any one selected from a sheet, a thin film, a woven fabric and a nonwoven fabric. Any material having electrochemical stability in water can be used. Preferably, a porous support of a polymer material is used. Any support that can make the porosity between ion exchange membranes without limitation is usable without limitation.

The method of attaching the ion exchange membrane of the present invention to the porous support may be a method using an adhesive or a pressure sensitive adhesive, a method of curing an ion exchange solution, or a method using a binder mixture, but the present invention is not limited thereto.

For example, it is preferable to use an epoxy adhesive. However, since ions can be introduced into and out of the porous support through the ion exchange membrane and the external fluid can not flow into the porous support and can maintain its shape It can be used without limitation.

The ion exchange solution is cured by applying an ion exchange solution of the same polarity to the cation exchange membrane and the anion exchange membrane in a thin layer of 1 to 30 μm and drying at room temperature to 150 ° C. until there is no flow property but sticky property and then attached to the porous support It is possible to use a heater, a hot air, an IR, and a UV drying method. However, the present invention is not limited thereto.

The method of using the mixture of the binder may be a method of kneading and applying the ion exchange resin powder and the binder mixture, and the coating method may be a melt extrusion coating, a calendering coating, a spray coating, a dip coating, a knife casting, Coating, and the like. However, the present invention is not limited thereto, and may include all application methods for achieving the object of the present invention. It is preferable that the coating thickness is in the range of 10 to 100 μm to improve the desalination efficiency while reducing the electrical resistance of the desalting sheet Do.

 The ion exchange resin powder and binder mixture of the present invention can be formed on a porous support using a conventionally known melt extrusion method. The melt extrusion method includes a T-die casting method and an inflation method. In order to form an ion exchange membrane layer on a porous sheet, a T-die casting method is preferable. As a device for melting the ion exchange resin powder and the binder mixture, a commonly used extruder may be used.

The extrusion temperature is preferably 100 to 300 ° C, more preferably 120 to 150 ° C. When the extrusion temperature is in the above range, balance of the ion exchange membrane layer of the obtained desalting sheet, adhesion, adsorption / desorption characteristics, and the like can be improved.

The air gap (distance until the molten coating layer is discharged from the die and contacted with the cooling roll) is preferably 0.1 to 100 mm, more preferably 3 to 30 mm. When the air gap is in the above range, the orientation relaxation deviations due to the heat of the resin during the slow cooling process between the air gaps (influences of the ambient environment of the air gap, The effect of the difference) can be suppressed to be small, and further, it is possible to suppress an abrupt increase in the film thickness of the end portion of the ion exchange membrane layer caused by the neck phosphorus.

The method of cooling the molten mixture of the ion-exchange resin powder and the binder mixture extruded from the die can be conventionally known methods and is generally cooled with a cooling roll. The number of the cooling rolls may be two or more depending on the discharge amount of the molten material or the speed of taking-out, and it is preferable to use a plurality of cooling rolls to cool the both sides of the desalted sheet coated with the molten material therebetween. The drawing speed is preferably from 0.2 to 100 m / min, more preferably from 1 to 90 m / min, though it varies depending on the apparatus such as the extruded amount of the molten metal or the width of the die. When the take-out speed is in the above-mentioned range, an ion exchange membrane having a desired thickness can be obtained. It is preferable to adjust the rotation speed of the cooling roll, the pinch roll, the winding roll, and the like so as not to be substantially stretched.

The present invention may include forming a channel patterning on the surface of the ion exchange membrane. By forming a flow path pattern, the module can be easily manufactured by stacking without a separate spacer.

The flow path patterning may be performed by a printing method such as a printing method or a lithography method, and a flow path may be formed by attaching a porous sheet. In the melt-extrusion coating, A T-die having a pattern may be used to form the flow path, but the present invention is not limited thereto.

Printing method As the patterning material of the channel, a material suitable for the patterning of the channel may be selected according to a method of patterning the channel in the ion exchange membrane. For example, the material may be selected from the group consisting of an oil / inorganic hardened body, a polymer hardened body, But is not limited thereto.

Printing Technique As a more specific example of the patterning method of the channel, screening printing is performed by putting a silk cloth or other screen on the frame, blocking the screen image of the portion other than the image by a manual operation or a method of photographing, A nylon, a deadron fiber, or a mesh made of stainless steel is spread on a frame and the four corners are tightly fixed, and then the ink is extruded through a screen or an optical method, To form a printing frame so as to be printed or coated only with a flow pattern or to be convex or concave on a flat sheet to be printed or coated with ink or a coating liquid. But it is not limited thereto.

In the method of attaching the porous sheet, it is preferable to use a woven fabric or a nonwoven fabric of a polymer material, but any material can be used without limitation as long as it can bond well with an ion exchange membrane of a desalting sheet to form a flow path.

 Although the thickness of the porous sheet is not limited within the range of attaining the object of the present invention, the thickness is preferably in the range of 20 to 2,000 mu m, more preferably 70 to 250 mu m. When the thickness of the porous sheet is 20 mu m or less, When the laminate is laminated after being attached to the exchange membrane layer, the flow channel through which the fluid can flow is too small to allow the fluid to flow, which may cause high pressure or frequent clogging during operation. In case of 2,000 μm or more, The ion removal efficiency becomes lower than the voltage.

When a flow path is formed by using a T-die having a flow path pattern in melt extrusion coating of the ion exchange resin powder and a binder mixture, a T-die is formed to form a concave surface and a convex surface in the coating layer By adjusting the thickness of the coating layer, a stripe flow path can be formed, and a flow path pattern can be formed on the melt compression cooling roll to form a flow path by compressing the ion exchange membrane layer. However, the present invention is not limited thereto.

The pattern of the flow path can change the direction of the flow and enlarge the length of the flow path or adjust the flow direction according to the flow amount. The flow pattern can be formed into various forms such as combs, wavy patterns, stripes, grid patterns, Form. It may also be formed in various shapes such as triangular, semi-elliptical, semicircular, trapezoidal, square, conical, and cylindrical shapes depending on the convex shape of the channel, but is not limited thereto.

Although the size and shape of the flow path formed in the electrode according to the present invention are not limited within the scope of attaining the object of the present invention, the flow path depth is preferably in the range of 5 to 100 mu m, more preferably 30 to 60 mu m, When the depth is 5 μm or less, if the positive electrode and the negative electrode are laminated, the distance between the positive electrode and the negative electrode is too short to allow the fluid to flow, which may cause high pressure or frequent clogging during operation. The ion exchange membrane layer can not be formed in the concave portion of the porous support layer, and the ions can not be concentrated on the porous support layer and can not serve as a desalting sheet.

The width of the flow path is preferably in the range of 10 to 5,000 mu m, more preferably 50 to 200 mu m, and when the flow path width is 10 mu m or less, the width of the flow path is too narrow, The pressure may be lowered. However, since the convex portions are overlapped on the concave portion of the flow path, it is difficult to form a uniform flow path.

In addition, the present invention may include a desalting sheet and a desalting sheet module manufactured by the above manufacturing method.

FIG. 4 is an exploded view of a cylindrical de-ionization sheet module of the roll type according to the present invention, FIG. 5 is a sectional view showing the structure of a desalination sheet in the cylindrical de- FIG. 6 is a view showing a method of manufacturing a desalination sheet roll for manufacturing a cylindrical desalination sheet module according to the present invention, and FIG. 7 is a view showing an assembly of a cylindrical desalination sheet module according to the present invention.

As shown in FIG. 4, the cylindrical desalination sheet module of the present invention has cation exchange membranes 102 and anion exchange membranes 103 before and after one porous support 101, respectively, and at the same time, channel patterns 104 and 105 are provided A porous tube 110 in which one or more sheets of the desalination sheet 100 having an integral structure are stacked so as to face the cation exchange membrane 102 and the anion exchange membrane 103 and wound in a roll shape at a constant pressure, And a non-woven fabric 120 for fixing the integral desalination sheet 100 wound in the form of a roll so as to maintain a roll shape. One of the wound desalination sheets has no holes and is brought into close contact with the module case, (130) having two O-rings (131), and the other has a drain port (142) capable of discharging water out of the porous tube to the outside, and raw water and process water are mixed A deionization sheet coated with an epoxy or urethane adhesive is molded on the plugs 130 and 140 so that the fluid can flow in one direction from the outside to the inside, The cylindrical module case 500 is assembled by inserting the desalination sheet roll 300 thus formed into the cylindrical module case 500. The cylindrical module case 500 has a negative electrode 531 on the inner side for applying electricity, And a module case cap 550 and an inlet port 510 and an outlet port 520 are provided in the module case.

5 and 6 illustrate the structure and assembly of the desalination sheet roll in the cylindrical desalination sheet module according to the present invention. The structure of the desalting sheet roll is shown in FIG. 5 and FIG. 6, A desalting sheet having an anion exchange membrane layer 102 and an anion exchange membrane layer 103 is laminated on the cation exchange membrane layer 102 and the anion exchange membrane layer 103 so as to face each other, Roll, and then a woven fabric or a nonwoven fabric 120 which can pass through the water can be wound around the deionized sheet 100 so that the deionized sheet 100 can be held in a roll form. One of the deionized sheet rolls has no hole, One end of the stopper 130 has two O-rings 131 to prevent water from being leaked out to the outside, and the other end has a hole 142 through which water out of the porous tube can be discharged out. And process water A desalination sheet roll 300 is formed so that a deionization sheet coated with an epoxy or a urethane adhesive can flow a fluid in one direction from the outside to the inside .

7 is a view showing an assembled view of a cylindrical de-ionization sheet module according to the present invention, in which a desalting sheet coated with an epoxy or urethane adhesive is molded into caps 130, 140, and a desalting sheet roll The desalination sheet roll 300 thus produced discharges the treated water or concentrated water to the center of the negative electrode 531 and the center electrode 531 so as to apply electricity in the cylindrical module case 500 having the inlet 510 The deodorization sheet roll 300 is assembled to the module case 500 constituting the flow path 540 and the positive electrode 530 and the module case plug 550 is connected to the outlet port 520 of the module case and the o- So that raw water and process water are not mixed with each other.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail with reference to examples of a method for producing a desalted sheet and a desalting sheet module of the present invention. However, the following examples are only illustrative of the present invention in more detail, and the present invention is not limited by the following examples.

[Production Example 1] - Desalting sheet made of ion exchange solution

The ion exchange membranes were prepared by casting after preparing cation exchange solution and anion exchange solution as follows. The cation exchange solution was prepared by mixing 1.0 g of polystyrene (cation exchange capacity = 1.5 meq / g) having a cation exchanger prepared through a sulfonation reaction and 20 g of dimethylacetamide (DMAc) to prepare a polymer solution, The cation exchange solution was cast on a glass plate and dried in an IR drier at 30 ° C for 30 minutes, at 50 ° C for 60 minutes and at 80 ° C for 2 hours to prepare a cation exchange membrane. Anion exchange solution was prepared by anion exchange (Anion exchange capacity = 1.2 meq / g) and 20 g of dimethylacetamide were mixed to prepare a polymer solution. The anion exchange solution was cast on a glass plate, and then dried in an IR drier at 30 DEG C for 30 minutes , And dried at 50 DEG C for 60 minutes and at 80 DEG C for 2 hours to prepare an anion exchange membrane.

The desalting sheet was prepared by applying a porous support (thickness: 200 μm, PP, Nanyang Nonwoven Co., Ltd.) between the cation exchange membrane and the anion exchange membrane prepared above and applying the edge with an epoxy adhesive (Devcon®, ITW Consumer Inc.) And adhered and cured to be sealed.

When a hot melt adhesive was sprayed on the desalted sheet at a high temperature and high pressure air (190 ° C, 7.5 atm), the nylon woven fabric having a pore structure distributed on a desalting sheet and having a thickness of 100 μm and 80 mesh And the sheet was heated and closely contacted with a roll press at 80 ° C to produce an integral desalinization sheet having a flow path.

[Manufacturing Example 2] - Desalting sheet made by coating ion exchange solution

The cation exchange solution prepared in [Preparation Example 1] was cast on a PET film and dried at 30 ° C. for 30 minutes and at 50 ° C. for 90 minutes using an IR drying lamp. When the film was sticky, (Thickness: 200 탆, PP, Nanyang Nonwoven Fabric Co., Ltd.) was placed on the top of the nonwoven fabric so that it could be adhered only to the outer side without penetrating into the nonwoven fabric. The anion exchange solution prepared in [Preparation Example 1] was cast on a PET film, and dried using an IR drying lamp at 30 ° C for 30 minutes and at 50 ° C for 90 minutes to remove sticky sticky The nonwoven fabric having the cation exchange membrane layer formed thereon is placed so as to be in contact with the nonwoven fabric so that the nonwoven fabric can be bonded only to the outside without penetrating into the nonwoven fabric And the cation exchange membrane layer and the anion exchange membrane layer on the edge are closely contacted with each other. Then, the membrane is completely dried at 80 ° C by an IR drying lamp and separated from the PET film to prepare a desalted sheet.

When a hot melt adhesive was sprayed on the desalted sheet at a high temperature and high pressure air (190 ° C, 7.5 atm), the nylon woven fabric having a pore structure distributed on a desalting sheet and having a thickness of 100 μm and 80 mesh And the sheet was heated and closely contacted with a roll press at 80 ° C to produce an integral desalinization sheet having a flow path.

[Production Example 3] - Deionization sheet made of ion-exchange resin powder and binder mixture

The cation exchange resin (Trilite CMP28, Samyang Corp.) and the anion exchange resin (Trilite AMP28, Samyang Corp.) were milled at 1700 rpm using an air jet mill (Model: NETSCH-CONDUX, Netsch) Mu m) and 2.0 mu m (maximum 5.5 mu m). The thus prepared cation exchange resin powder or anion exchange resin powder was mixed so as to have a linear low density polyethylene (LLDPE Lotte Chemical U8835) in an amount of 52 wt% and 48 wt%, respectively, relative to 100 wt% of the mixture, KMT, Korea) and rotated at 25 RPM for 1 hour and then kneaded at 30 RPM for 1 hour to prepare uniform composition of cation exchange resin powder and linear low density polyethylene, uniform composition of anion exchange resin powder and linear low density polyethylene.

The desalination sheet was obtained by forming a desalting sheet on a non-woven fabric by using a single-screw extruder (screw diameter of 32 mm?) With a vacuum vent equipped with a coat hanger type T die of a 150 mm width in a leaf disk shape, a cooling compression roll And a winder (tension adjustable). Extruder cylinder temperature of 120 占 폚, T-die temperature of 120 占 폚, flat cooling compression roll temperature of 60 to 65 占 폚, T-die lip opening of 0.1 mm, air gap of 20 mm and discharge speed of 3 kg / A different ion exchange membrane was formed on both sides of the membrane.

When a hot melt adhesive was sprayed on the desalted sheet at a high temperature and high pressure air (190 ° C, 7.5 atm), the nylon woven fabric having a pore structure distributed on a desalting sheet and having a thickness of 100 μm and 80 mesh And the sheet was heated and closely contacted with a roll press at 80 ° C to produce an integral desalinization sheet having a flow path.

[Manufacturing Example 4] - A flow pattern type desalination sheet made of a mixture of an ion exchange resin powder and a binder

The cation exchange resin (Trilite CMP28, Samyang Corp.) and the anion exchange resin (Trilite AMP28, Samyang Corp.) were milled at 1700 rpm using an air jet mill (Model: NETSCH-CONDUX, Netsch) Mu m) and 2.0 mu m (maximum 5.5 mu m). The thus prepared cation exchange resin powder or anion exchange resin powder was mixed so as to have a linear low density polyethylene (LLDPE Lotte Chemical U8835) in an amount of 52 wt% and 48 wt%, respectively, relative to 100 wt% of the mixture, KMT, Korea) and rotated at 25 RPM for 1 hour and then kneaded at 30 RPM for 1 hour to prepare uniform composition of cation exchange resin powder and linear low density polyethylene, uniform composition of anion exchange resin powder and linear low density polyethylene.

The desalination sheet was obtained by forming a desalting sheet on a non-woven fabric by using a single-screw extruder (screw diameter of 32 mm?) With a vacuum vent equipped with a coat hanger type T die of a 150 mm width in a leaf disk shape, a cooling compression roll And a winder (tension adjustable). Extruder cylinder temperature of 120 占 폚, T-die temperature of 120 占 폚, flat cooling compression roll temperature of 60 to 65 占 폚, T-die lip opening of 0.1 mm, air gap of 20 mm and discharge speed of 3 kg / A different ion exchange membrane was formed on both sides of the membrane.

A monolithic desalination sheet having a stripe flow path pattern was formed at the same time as the formation of the ion exchange membrane layer by tumbling on a cooling compression roll having a uniform flow path pattern having a width of 70 mu m, a height of 40 mu m and an interval of 200 mu m, Respectively.

[Examples 1 to 4] Desalting sheet module

As shown in FIG. 2, the desalting sheets prepared in [Manufacturing Examples 1 to 4] were stacked in three layers of 5 x 20 cm 2, which had a flow path pattern so that the cation exchange membrane and the anion exchange membrane of the desalting sheet faced each other The anion exchange membrane of the laminated desalted sheet was constructed so that the outer surface of the anion exchange membrane was opposite to the outer surface of the cation exchange membrane. At this time, the fluid was sealed with epoxy on both sides so that the fluid could escape from one direction to the other of the desalting sheet, and the module was constituted to evaluate the desalting characteristics.

A 250 mg / L NaCl solution was supplied at a rate of 90 mL / min while the electrode potential was kept constant at 4.5 V. The total dissolved solids (TDS) of the effluent was measured and the desalting efficiency was analyzed. The results of desalting experiments are shown in Table 1 as the salt removal rate (%).

[Comparative Examples 1 to 4] A desalting sheet module in which a flow path was made of a spacer

As shown in FIG. 2, the desalting sheets prepared in [Preparation Examples 1 to 4] were laminated so that the cation exchange membrane layer and the anion exchange membrane layer of the desalting sheet were opposed to each other and the fluid was allowed to flow between the desalting sheets. (Nylon 6, thickness: 100 탆, 80 mesh) were placed to laminate three ion exchange sheets. The anion exchange membrane of the laminated desalted sheet was constructed so that the outer surface of the anion exchange membrane was opposite to the outer surface of the cation exchange membrane. At this time, the fluid was sealed with epoxies on one side of the laminated desalination sheet so that the fluid could escape through the spacer in the other direction.

A 250 mg / L NaCl solution was supplied at a rate of 90 mL / min while the electrode potential was kept constant at 4.5 V. The total dissolved solids (TDS) of the effluent was measured and the desalting efficiency was analyzed. The results of desalting experiments are shown in Table 2 as the salt removal rate (%).

division Example 1 Example 2 Example 3 Example 4 Salt Removal Efficiency (%) 85.1 88.6 71.4 75.2

division Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Salt Removal Efficiency (%) 83.3 87.6 70.8 73

As a result of conducting a desalination test on the module made by Examples 1 to 4, as shown in [Table 1], [Example 2]> [Example 1]> [Example 4]> [Example 3] , And it was confirmed that it has excellent salt removal efficiency. Particularly, since the porous support and the ion exchange solution adhere to each other, the separation between the cation exchange membrane and the anion exchange membrane is small, and the resistance of the ion exchange membrane is the smallest, , And [Example 3] was low because the ion exchange membrane was made of a mixture of an ion exchange resin and a polyethylene binder, so that the membrane resistance was high and the removal efficiency was low. However, since the ion exchange membrane layer was formed by pressing a pattern on the ion exchange membrane layer by roll pressing, the membrane of Example 4 in which an ion exchange membrane was formed of the same ion exchange resin and a polyethylene mixture showed better salt removal efficiency than Example 3, The removal efficiency was increased because the layer was thinned and the membrane resistance was lowered.

Further, as a result of conducting a desalination test on a module made by Comparative Examples 1 to 4, it can be seen that the desalting efficiencies are similar to those of Examples 1 to 4 as shown in [Table 2]. This indicates that the integrated desalination sheet of the present invention is excellent in the desalting efficiency compared with the comparative example, even when a channel is formed without using a spacer. In addition, it is expected that if the module is integrated, the productivity of the module can be improved by improving the assemblability of the module.

[Comparative Example 5] Electrolytic desalting electrode manufacturing

1.2 g of polyvinylidene diprolide (PVdF, Aldrich, Mw = 370,000) and 40 g of dimethylacetamide were mixed to prepare a polymer solution. To the polymer solution, activated carbon powder (P-60, Surface area = 1600 m 2 / g) were mixed to prepare an electrode slurry.

The prepared slurry was coated on a conductive graphite sheet (130 占 퐉 thick, Dongfang Carbon Co., Ltd., Cat. No. F02511C) with a doctor blade so that the coating layer had a thickness of 200 占 퐉 and then dried at 70 占 폚 Dried for 30 minutes, coated on the backside with a doctor blade to a coating layer thickness of 200 μm, and dried at 70 ° C. for 30 minutes to prepare a carbon electrode having an active layer.

The cation exchange membrane and the anion exchange membrane prepared in Preparation Example 1 were placed on both sides of the carbon electrode, respectively, and pressed by a roll press at 70 캜 to prepare a storage desalting electrode. The module was also prepared in the same manner as in Example 1 above.

FIG. 3 shows the change curves of TDS according to desorption time according to [Example 1] and [Comparative Example 5]. In the case of the storage type desalting electrode [Comparative Example 5], the initial desalination performance is excellent at 32 ppm, The desalting efficiency of the desalting sheet [Example 1] was lower than that of the storage desalting at about 49 ppm, but the removal efficiency was almost It can be confirmed that the removal efficiency is excellent at 69 ppm when the adsorption time is 5 minutes. From these results, it can be confirmed that the treatment capacity is improved by 40% or more at the same concentration.

100: desalting sheet
101: Porous support
102: Cation exchange membrane
103: Anion exchange membrane
104, 105: Euro pattern
110: Porous tube
120: Nonwoven fabric
130, 140: Plug
131, 141: O-ring
142: Drain
300: desalinized sheet roll
500: Module case
510: inlet
520: Outlet
530: positive polarity
531: negative polarity
540: Euro
550: Module plug

Claims (11)

Forming an ion exchange membrane using an ion exchange solution or an ion exchange resin powder; Attaching the ion exchange membrane to both sides of the porous support; And forming a channel patterning on the surface of the ion exchange membrane. The method according to claim 1,
Wherein the ion exchange solution is formed by dissolving a polymer resin having a cation or anion exchanger in an organic solvent to form an ion exchange membrane. The method according to claim 1,
Wherein the ion-exchange resin powder is obtained by mixing a polymer resin having a cationic or anion-exchange group in powder form with a binder to form an ion-exchange membrane. 3. The method of claim 2,
The polymer resin may be any one selected from the group consisting of polystyrene, polysulfone, polyisocyanurate, polyamide, polyphenylene oxide, polyester, polyimide, polyether, polyethylene, polytetrafluoroethylene and polyglycidyl methacrylate By weight based on the total weight of the desalting sheet. The method according to claim 1,
Wherein the porous support has any one of a sheet, a thin film, a woven fabric, and a nonwoven fabric of a polymer material. The method according to claim 1,
The method for attaching the ion exchange membrane to a porous support is a method of using an adhesive, a method of curing an ion exchange solution, or a method of using a binder mixture. The method according to claim 1,
Wherein the channel patterning has a depth of 5 to 100 탆 and a width of 10 to 5,000 탆. A desalting sheet produced by the method of any one of claims 1 to 7. A desalting sheet comprising at least one desalting sheet of claim 8;
A porous tube in which the desalting sheet is wound in a cylindrical shape;
A desalination sheet module case for allowing the desalination sheet to be installed therein; And
A module cap sealing the module case;
The desalination sheet module comprising: 10. The method of claim 9,
Wherein the desalting sheet has a structure in which one or more layers are stacked, and the cation exchange membrane and the anion exchange membrane are laminated in a manner facing each other and wound on the porous tube. 10. The method of claim 9,
Wherein the module case further comprises a positive electrode, a negative electrode, an inlet and an outlet.

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