KR101628899B1 - Liquid Treating Chemical Filter Using Sulfonated Nano-Fiber Web and Method of Manufacturing the Same - Google Patents

Abstract

TECHNICAL FIELD The present invention relates to a liquid treatment chemical filter using a sulfonated nanofiber web and a method for producing the same, and more particularly, to a nanofiber web having three-dimensional fine pores, which performs a water treatment filter function capable of surface filtration and deep filtration It is also possible to filter specific ions of chemical substances contained in the liquid by introducing sulfonic acid groups introduced into the multi-layer nanofiber web, and the inside of the nanofiber of the multi-layer nanofiber web, and the nanofibers inside the first and second nanofiber web The ion exchange resin particles dispersed outside the fiber participate in the filtering of specific ions of the chemical substance contained in the liquid, thereby improving the filtering efficiency.

Description

TECHNICAL FIELD [0001] The present invention relates to a liquid treatment chemical filter using a sulfonated nanofiber web,

TECHNICAL FIELD The present invention relates to a liquid treatment chemical filter using a sulfonated nanofiber web and a method for producing the same, and more particularly, to a microfluidic structure having a three-dimensional network structure of a nanofiber web, which functions as a water treatment filter capable of surface filtration and deep filtration The ion exchange resin particles dispersed in the nanofibers of the multi-layer nanofiber web and the ions dispersed in the nanofibers inside the first and second nanofiber webs A liquid chemical filter using a sulfonated nanofiber web that improves the filtering efficiency and imparts various functions to the filter by having a chemical filter function for filtering specific ions of the chemical substance contained in the liquid by the exchange resin particles And a process for producing the same.

Recently, the problem of environmental pollution has been greatly increased due to the expansion of industrial scale due to economic growth and the concentration of large cities and factories. Water pollution has become a serious problem, and in the case of drinking water, it is essential to purify water through a water purifier.

The water purifier is essentially provided with a filter for filtering raw water, and the filter is formed by filtering water such as a nonwoven filter, an activated carbon filter, an activated carbon fiber (ACF) filter, a hollow fiber membrane filter, an ion exchange resin filter, Various water filters are applied according to the method and step.

Currently, carbon filters are used as materials or filters that remove heavy metals and metallic ion components present in water from water purifiers.

Activated carbon is a special carbon that is calcined at high temperature using mainly coconut shell, wood, coal, etc. as a raw material. It means a collection of amorphous carbon with well-developed fine pores of molecular size formed during the activation process. It is possible to adsorb and remove various pollutants present in the water due to the adsorption characteristics based on the wide internal surface area of activated carbon, and it is widely used in this field due to excellent residual chlorine, organic matter adsorption and deodorization performance.

In general, activated carbon is an adsorbent having an internal surface area of 800 to 1200 m < 3 > / g. However, most of the adsorption occurs when the functional group of the carbon atom existing in the activated carbon exerts an attractive force on the surrounding liquid or gas, Is a physical adsorption. There is a need for a filter capable of chemically adsorbing specific ions rather than physical adsorption, thereby removing heavy metals and metallic ion components present in water.

In general, the treatment methods of water pollutants include coprecipitation using wastewater treatment coagulant, flotation method by specific gravity difference, bioconcentration method, and ion exchange sorption method, but ion exchange sorption method is known as the most effective method.

Korean Patent Laid-Open Publication No. 2011-85096 proposes a composite filter in which activated carbon fibers and ion exchange fibers are laminated on the side wall of the housing. However, the size of the filter is large in the form of a composite filter capable of downsizing the water purifier, to be.

Korean Patent Registration No. 507969 discloses a method of producing a web by forming a web of ion exchange fiber on an ion exchange nonwoven fabric, sprinkling ion exchange resin on the web, placing an ion exchange nonwoven fabric thereon, There has been proposed a technique of removing ionic gas such as acidic or alkaline present in a clean room of a semiconductor manufacturing process. However, it has a disadvantage in that it can not filter ionic gas and filter chemical ions contained in the liquid.

On the other hand, microporous membranes have been used in material separation processes and are manufactured by various methods to have various structures and functions. Among them, research on water treatment membranes has been started for a long time.

BACKGROUND ART [0002] Membrane technology has been widely used in the field of liquid treatment such as removal of contaminants in liquids or separation, concentration and recovery of useful substances as membrane manufacturing technology and application technology are developed remarkably.

Membrane technology is replacing existing technologies due to constant performance and stability due to membrane pore size, convenience due to automation, and simple system.

Conventionally, membranes used in liquid filters include porous membranes and calendered nonwovens.

The porous membrane is a membrane that forms a membrane by using a polymer material such as PTFE, nylon, or polysulfone, and then forms pores by a chemical or physical method. Since the pore structure at this time is a closed pore structure having a two-dimensional shape, the filter efficiency is low.

In the past, when a hydrophobic polymer such as PTFE is used, since the pore structure has a closed pore structure having a two-dimensional shape, since the liquid does not pass therethrough, it is used as a filter requiring pressure, , And low volume is pointed out as a problem.

Furthermore, the thickness of the porous membrane is thicker because the thickness of the porous material is 100 μm depending on the material. Therefore, there is a problem that it is difficult to bend the porous membrane filter material and to introduce a large amount of arsenic into the filter.

On the other hand, the calendered nonwoven fabric forms fibers by, for example, melt-blown spinning of polypropylene as a polymer material, but since the size is in micro units, it does not have microscopic pores and fibers are not uniformly distributed The pores are uneven, and the pollutants are concentrated through the large pores and the filter efficiency is low.

In addition, the calender nonwoven fabric has an average pore size of 5 to 20 μm, and excessive calendering is required to reduce the average pore size of the filter to 3 μm or less. However, since excessive calendering prevents voids and reduces porosity, if the calendered nonwoven fabric is used as a liquid treatment filter, the filter pressure is high and the pores are blocked quickly, which causes problems in the filter life.

Therefore, even if a liquid processing module is manufactured using existing membrane technology, there is a problem that fluid flow is reduced due to membrane clogging and operation pressure is increased.

This clogging phenomenon is particularly serious in high concentration fluids, and it is impossible to apply the membrane technology to high concentration and high turbidity fluids, and the pores are gradually widened, resulting in poor durability.

Accordingly, it is urgently required to develop a membrane having a high filtration efficiency and a high filtration efficiency depending on the pore size as a thin membrane having a micropore structure so that it can be used for liquid treatment.

Korean Patent Laid-Open Publication No. 2008-60263 discloses a nonwoven fabric comprising at least one nanofiber layer of polymer nanofibers having an average fiber diameter of less than about 1 占 퐉 and having an average flow pore size of about 0.5 占 퐉 to about 5.0 占 퐉 , A solids content of from about 15% to about 90% by volume, and a flow rate of water through the medium at differential pressures of 10 psi (69 kPa) greater than about 0.055 L / min / cm ² .

The manufacturing method of the filtration medium proposed in the above-mentioned Patent Publication No. 2008-60263 includes a radiation beam including at least one radiation beam including a radiation nozzle, a blowing gas injection nozzle and a collector, Blown together with a blowing gas discharged from a gas injection nozzle while compressing and discharging a polymer solution from a spinning nozzle to form a fibrous web of nanofibers using a fine fiber spinning apparatus in which a high voltage electric field is maintained, And is collected on the moving collecting device by a single pass under the radiation beam.

In addition, in JP-A-2008-60263, there is illustrated an example of forming a web by spinning nanofibers using a solution containing 24% by weight of nylon in formic acid as a polymer solution by an electroblow spinning or an electric blowing method .

However, the method of forming the fibrous web of nanofibers in the above-mentioned Patent Publication No. 2008-60263 can not be said to be a manufacturing technique using a multi-hole spinning pack. In order to increase the productivity, when a nanofiber web is manufactured by an electrospinning method using an electrospinning device equipped with a plurality of spinning nozzles in a plurality of rows and columns and using a multi-hole spinning pack in which each nozzle is spinning, The spinning solution containing the polymer in an amount of 10 to 30% by weight has a problem in that the viscosity of the spinning solution is increased to cause solidification on the surface of the solution, making it difficult to spin for a long period of time and increase the fiber diameter.

Moreover, ultrafine fiber webs obtained by electrospinning have a problem in that when the pretreatment process for appropriately adjusting the amounts of the solvent and moisture remaining on the web surface is not performed before calendering, the strength of the web is weakened Or if the volatilization of the solvent is made too slow, the phenomenon of melting of the web may occur.

On the other hand, a filter material for a liquid filter using electrospun nanofiber web described in Korean Patent Publication No. 2012-02491 filed by the present applicant, a method for producing the same, and a liquid filter using the filter material have a three-dimensional microporous structure So that the filter efficiency can be maximized with high efficiency and long life.

 Therefore, it is possible to produce a filter for a liquid using such a multi-layered nanofiber web. However, the filter for liquid does not have a filter function of a chemical substance contained in the liquid, so that specific ions of a chemical substance contained in the liquid are filtered It is required to carry out research in a direction in which a liquid filter can be manufactured so as to have the function of being able

The inventors of the present invention have conducted research with a feature of filtering a specific ion of a chemical substance in a liquid filter using a multi-layered nanofiber web according to this direction, and have found that a more economical liquid chemical compound Thus completing the present invention.

Korea Patent Publication No. 2011-85096 Korean Patent No. 507969 Korean Patent Publication No. 2008-60263 Korean Patent No. 2012-02491

As described above, the filter to which the ion-exchange fiber is applied is large in size and does not filter the chemical ions contained in the liquid. The filtration membrane of the liquid treatment membrane has a low filtering efficiency, and the fibrous web obtained by electrospinning has a fibrous shape There is a problem that can not be made.

SUMMARY OF THE INVENTION The present invention has been made in view of the problems of the prior art, and it is an object of the present invention to provide a nanofiber web having three-dimensional micropores capable of surface filtration and deep filtration of a liquid and introducing a sulfonic acid group introduced into the multi- A liquid-treated chemical filter using a sulfonated nanofiber web capable of filtering specific ions of a chemical substance contained in a liquid, and a method for producing the same.

Another object of the present invention is to provide a method for filtering specific ions of a chemical substance contained in a liquid by ion exchange resin particles dispersed in nanofibers of a multilayer nanofiber web and nanofibers inside the first and second nanofiber webs And to provide a method of manufacturing a liquid chemical filter using the sulfonated nanofiber web.

It is still another object of the present invention to provide a liquid treatment chemical filter using a sulfonated nanofiber web capable of improving the reliability of chemical filtering by preventing movement of ion exchange resin particles that can be flowed by electric spraying, .

It is still another object of the present invention to provide a liquid chemical filter using a sulfonated nanofiber web capable of performing various filtration functions by designing the thickness of the web and the diameter of the nanofibers differently, and a method for manufacturing the same.

It is another object of the present invention to provide a method of forming nanofibers or nanofibers using a sulfonated nanofiber web that can guide nanofibers or injected beads emitted by air spinning and spraying to minimize spinning or jetting trouble Liquid chemical filter and a method of manufacturing the same.

It is another object of the present invention to provide a method for producing a liquid treating chemical using a sulfonated nanofiber web capable of preventing the deterioration of the filter efficiency due to the thin layer and thin structure, Filter and a method of manufacturing the same.

It is still another object of the present invention to provide a liquid treatment chemical filter using a sulfonated nanofiber web having a large specific surface area and a small average pore size and a large maximum pore size by using a nanofiber web having a three- And to provide a method for manufacturing the same.

It is still another object of the present invention to provide a nanofiber web having a three-dimensional network structure as a membrane, which has a large amount of impurity particles, a high impurity removal rate, Filter and a method of manufacturing the same.

Another object of the present invention is to provide a liquid treatment chemical filter using a sulfonated nanofiber web having a high pore size and a high flow rate by using a nanofiber web having a three-dimensional network structure as a membrane, and a process for producing the same There is.

In order to achieve the above object, according to an embodiment of the present invention, nanofibers obtained by electrospinning a polymer material are stacked in a plurality of layers and have fine pores, and at least one of the nano- A multi-layer nanofiber web in which the diameter of the fiber is different from the diameter of the nanofiber of the remaining layer; And a sulfonic acid group introduced into the multi-layered nanofiber web. The present invention also provides a liquid-treated chemical filter using the sulfonated nanofiber web.

According to an embodiment of the present invention, there is provided a multi-layer nanofiber web having fine pores, in which nanofibers obtained by electrospinning a polymer material are laminated; An ion exchange resin particle dispersed in the inside or outside of the nanofiber; And a sulfonic acid group introduced into the multi-layered nanofiber web. The present invention also provides a liquid-treated chemical filter using the sulfonated nanofiber web.

And a support is formed on the upper part of the multi-layered nanofiber web, the lower part of the multi-layered nanofiber web, and both the upper part and the lower part of the multi-layered nanofiber web.

The ion exchange resin particles are characterized by particles of a porous organic polymer having ion exchange ability or particles of a copolymer of polystyrene and divinylbenzene.

Wherein when the ion exchange resin particles are dispersed in the nanofiber, a part of the ion exchange resin particles is exposed on the surface of the nanofiber.

According to an embodiment of the present invention, a first multi-layered nanofiber web having micropores, in which nanofibers obtained by electrospinning a polymer material are stacked, and micropores; Ion exchange resin particles dispersed in the first multi-layer nanofiber web and positioned outside the nanofibers; A second multi-layer nanofiber web laminated to the first multi-layer nanofiber web to prevent movement of the ion exchange resin particles; And a sulfonic acid group introduced into the first and second nanofiber webs. The present invention also provides a liquid treatment chemical filter using the sulfonated nanofiber web.

Wherein a support is formed on either one of the first multi-layered nanofiber web, the second multi-layered nanofiber web, and the first and second multi-layered nanofiber webs.

The liquid treatment chemical filter may be a flat plate type structure in which a plurality of the first and second nanofiber webs are laminated with the support or a roll type in which the first and second nanofiber webs Structure.

Wherein the ion exchange resin particles are cation exchange resin particles or anion exchange resin particles.

And the thickness of the first nanofiber web and the thickness of the second nanofibrous web are different from each other.

The diameter of the nanofiber of the first nanofiber web and the diameter of the nanofiber of the second nanofiber web are the same or different.

Wherein the average pore size of the first nanofiber web is greater than the average pore size of the second nanofiber web.

According to an embodiment of the present invention, there is provided a method of manufacturing a spinning solution, comprising: preparing a spinning solution by mixing a polymer material and a solvent; The spinning solution is electrospun with a plurality of spinning nozzles having at least one different diameter, and the nanofibers are stacked in a plurality of layers and have fine pores. The diameters of at least one layer of the nanofibers Forming a multi-layer nanofiber web different from the diameter of the nanofibers of the remaining layer; And introducing a sulfonic acid group into the multi-layered nanofiber web. The present invention also provides a method for producing a liquid-treated chemical filter using a sulfonated nanofiber web.

Wherein the ion exchange resin particles are further mixed in the step of mixing the polymer material and the solvent to prepare a spinning solution to produce a spinning solution.

The step of introducing the sulfonic acid group may include dipping the multi-layered nanofiber web into a solution in which a sulfonation reaction occurs in which one of concentrated sulfuric acid, fuming sulfuric acid, and chlorosulfonic acid is substituted with a hydrocarbon, And a step of attaching a sulfone group to the nanofibers of the nanofiber.

According to an embodiment of the present invention, there is provided a method for preparing a polymer solution, comprising: preparing a first spinning solution by mixing a polymer material and a solvent; Forming a first multilayer nanofiber web by first electrospinning the first spinning solution; Mixing the ion exchange resin particles with a solvent to prepare a solution for fractionation; Dispersing the ion exchange resin particles in the first multi-layered nanofiber web by electro-spraying the dispersion solution; Mixing a polymer material and a solvent to prepare a second spinning solution; Forming a second multi-layered nanofiber web on the first multi-layered nanofiber web in which the ion exchange resin particles are dispersed by second electrospinning the second spinning solution; And introducing a sulfonic acid group into the multi-layered nanofiber web. The present invention also provides a method for producing a liquid-treated chemical filter using a sulfonated nanofiber web.

And air is sprayed to prevent the emitted nanofibers and injected beads from being blown during the first and second electrospinning and the electrospinning.

The size of the beads adjacent to the first multi-layered nanofiber web is smaller than the size of the first bead sprayed.

The diameter of the nanofiber of the first nanofiber web and the diameter of the nanofiber of the second nanofiber web are the same or different.

After the introduction of the sulfonic acid group, a heat treatment process is further performed to improve the stability and durability of the nanofiber web.

As described above, in the present invention, the liquid can be subjected to surface filtration and deep filtration with a laminated structure of a multi-layered nanofiber web having three-dimensional micropores, and a sulfonic acid group introduced into the multi- Specific ions of matter can be filtered.

In the present invention, the sulfonic acid group introduced into the multi-layered nanofiber web, the ion exchange resin particles dispersed in the nanofibers of the multi-layer nanofiber web, and the ion exchange resin dispersed outside the nanofibers inside the first and second nanofiber webs By filtering specific ions of chemical material contained in the liquid as particles, the chemical filter efficiency can be improved and various functions can be imparted to the filter.

In the present invention, in order to prevent the movement of the ion exchange resin particles seated on the first nanofiber web by the electric spraying, the second nanofiber web may be laminated on the first nanofiber web to ensure the reliability of the chemical filtering .

In the present invention, the thickness of the first and second nanofiber webs and the diameter of the nanofibers may be designed differently to perform various filtering functions.

In the present invention, spinning or spraying while performing air injection can prevent the nanofibers or injection beads from flying, thereby minimizing radiation or jetting trouble.

In the present invention, nanofiber web having electrospinning three-dimensional fine pores is used as a membrane, and durability is good, and hydrophilic resin as well as hydrophilic resin can be applied due to capillary phenomenon.

In the present invention, because calendering is performed at a high temperature and a high pressure so as to have a fine pore size, the filter efficiency can be prevented from being reduced due to the thinness of the thickness and the multilayer structure.

In the present invention, when a nanofiber web having a three-dimensional network structure is used as a membrane, the specific surface area is large, the average pore is small, and the maximum pore is large.

In the present invention, the amount of trapping of the impurity particles is large, the impurity removal rate is high, and the filter filtering property is excellent.

In the present invention, it is possible to realize a liquid processing chemical filter having high pores and a high flow rate.

1 is a schematic view of an electrospinning device applied to a first embodiment of the present invention,
FIG. 2 is a flow chart of a manufacturing process of a liquid treatment chemical filter using a sulfonated nanofiber web according to the first embodiment of the present invention,
3 is a conceptual process sectional view for explaining an example method of introducing a sulfonic acid group into a multi-layered nanofiber web applied to the first embodiment of the present invention,
4A and 4B are conceptual process sectional views for explaining structural characteristics of an example of a multi-layered nanofiber web applied to the first embodiment of the present invention,
5 is a schematic view of an electrospinning and electrospray device applied to a second embodiment of the present invention,
FIG. 6 is a flow chart of a manufacturing process of a liquid treatment chemical filter using a sulfonated nanofiber web according to a second embodiment of the present invention,
7A to 7C are conceptual cross-sectional views illustrating a process for producing a nanofiber web having ion-exchange resin particles applied according to a second embodiment of the present invention,
FIG. 8 is a flowchart of a process that can be selectively added to the manufacturing process of the liquid processing chemical filter according to the first and second embodiments of the present invention.

In the present invention, a multi-layered nanofiber web is formed by mixing a polymer material and a solvent to prepare a spinning solution, electrospinning a spinning solution, introducing a sulfonic acid group into the multi-layered nanofiber web, Produce a filter.

In the present invention, a spinning solution is prepared by mixing a polymer material, ion exchange resin particles and a solvent, and electrospinning is performed using a multi-hole spinning pack having a plurality of rows and a plurality of rows to form a nanofiber web, A liquid chemical filter using a sulfonated nanofiber web is prepared by introducing a sulfonic acid group into the web.

In the present invention, a first spinning solution is prepared by mixing a polymer material and a solvent, a first spinning solution is first electrospun to form a first multi-layered nanofiber web, and ion exchange resin particles and a solvent are mixed to prepare a solution The ion exchange resin particles are dispersed in the first multi-layered nanofiber web by performing electrospray on the dispersing solution, the second spinning solution is prepared by mixing the polymer substance and the solvent, and the second spinning solution is mixed with the second electric spinning solution A second multi-layered nanofiber web is formed on the first multi-layered nanofiber web in which ion exchange resin particles are dispersed, and then a sulfonated polymer is introduced into the multi-layered nanofiber web to form a liquid-treated chemical filter using a sulfonated nanofiber web do.

Here, the injected ion exchange resin particles are dispersed in the first multi-layered nanofiber web, but the bonding force between the ion exchange resin particles and the first multi-layered nanofiber web can be reduced by the external force, and the second multi- Thereby making it possible to prevent the exchange resin particles from being separated from the first multi-layered nanofiber web.

Therefore, the multi-layered nanofiber web is formed by laminating nanofibers of a spun polymer material. In the nanofiber web, three-dimensional network-shaped micropores are formed, and when the treated water passes through the microporous web, Thereby filtering the fine nanoparticles of the nanoparticles. That is, surface filtration consisting of the surface layer and deep filtration consisting of the inner layer are made of nanofibers of polymeric material.

The fibers of the multi-layer nanofiber web and the ion exchange resin particles are attached with a sulfonic acid group (-SO ₃ H), and specific ions of the chemical substance contained in the ion exchange resin particles and sulfone groups are filtered.

In the present invention, a multi-layered nanofiber web is dipped into a solution in which a sulfonation reaction occurs in which one of concentrated sulfuric acid, fuming sulfuric acid, and chlorosulfonic acid is substituted with a hydrocarbon, To introduce a sulfonic acid group into the multi-layered nanofiber web.

In the present invention, after forming the first multi-layered nanofiber web and the second multi-layered nanofiber web, a liquid treatment chemical filter can be manufactured after the nonwoven fabric or the base paper is laminated as a support.

The nonwoven fabric usable herein may be any of a melt-blown nonwoven fabric, a spun bond nonwoven fabric, a thermal bond nonwoven fabric, a chemical bond nonwoven fabric, and a wet-laid nonwoven fabric as a support . The nonwoven fabric may have a fiber diameter of 40-50 mu m and a pore size of 100 mu m or more.

The polymeric material used in the present invention is capable of electrospinning, for example, a hydrophilic polymer and a hydrophobic polymer, and one or more of these polymers may be used in combination.

The polymer material usable in the present invention is not particularly limited as long as it is soluble in an organic solvent for electrospinning and is capable of forming nanofibers by electrospinning. For example, polyvinylidene fluoride (PVdF), poly (vinylidene fluoride-co-hexafluoropropylene), perfluoropolymers, polyvinyl chloride, polyvinylidene chloride or copolymers thereof, polyethylene glycol di Polyoxyethylene-polyoxypropylene oxide, polyethylene glycol derivatives including alkyl ethers and polyethylene glycol dialkyl esters, polyoxides including poly (oxymethylene-oligo-oxyethylene), polyethylene oxide and polypropylene oxide, polyvinyl acetate, poly (vinylpyrrolidone- Vinyl acetate), polystyrene and polystyrene acrylonitrile copolymers, polyacrylonitrile (PAN), polyacrylonitrile copolymers including polyacrylonitrile methyl methacrylate copolymers, polymethyl methacrylate, polymethyl methacrylate Acrylate copolymer or a mixture thereof.

Examples of usable polymer materials include polyamide, polyimide, polyamideimide, poly (meta-phenylene isophthalamide), polysulfone, polyetherketone, polyetherimide, polyethylene terephthalate, , Aromatic polyesters such as polyethylene naphthalate, polyphosphazenes such as polytetrafluoroethylene, polydiphenoxaphospazene, poly {bis [2- (2-methoxyethoxy) Polyurethane copolymers including polyether urethanes, cellulose acetate, cellulose acetate butyrate, and cellulose acetate propionate.

Of the above polymer materials, PAN, polyvinylidene fluoride (PVdF), polyester sulfone (PES) and polystyrene (PS) may be used alone or polyvinylidene fluoride PVdF) and polyacrylonitrile (PAN), PVDF, PES, PVdF and thermoplastic polyurethane (TPU) may be mixed and used.

Accordingly, the polymer usable in the present invention is not particularly limited to thermosetting and thermosetting polymers capable of electrospinning.

For the solvent to be mixed with the polymer substance for preparing the spinning solution, a mono-component solvent such as dimethylformamide (DMF) may be used. In the case of using the two-component solvent, the boiling point it is preferable to use a two-component solvent in which the higher and the lower one are mixed.

In the two-component mixed solvent according to the present invention, the high boiling point solvent and the low boiling point solvent are preferably mixed in a weight ratio of 7: 3 to 9: 1.

In the present invention, the ion exchange resin may be a cation exchange resin or an anion exchange resin.

That is, in the present invention, the ion-exchange resin particles may be defined as having an ion-exchangeable functional group on the inner surface and may include cation exchange resin, anion exchange resin, positive exchange resin and the like depending on the ion to be exchanged.

More specifically, in the present invention, PSDVB, which is a porous organic polymer having an ion exchange capacity or a copolymer of polystyrene and divinylbenzene, is made into particles, and the particles and a solvent are mixed to prepare a liquid dispersion.

1 is a schematic view of an electrospinning apparatus applied to the first embodiment of the present invention.

1, the electrospinning apparatus of the present invention includes a spinning liquid tank 1 for storing a polymer material, a spinning solution mixed with a solvent, and a plurality of spinning nozzles 41a, 41b, and 41c to which a high voltage generator (not shown) 41c, and 41d are arranged in a plurality of rows / a plurality of rows. The spinning liquid tank (1) may store a spinning solution in which ion exchange resin particles are further mixed.

The radiation pack 40 is disposed above a grounded collector 6 in the form of a conveyor moving at a constant speed and a plurality of spinning nozzles 41a, 41b, 41c and 41d are arranged at intervals And the plurality of spinning nozzles 41a, 41b, 41c, and 41d are arranged at intervals along the direction orthogonal to the traveling direction of the collector 6 (i.e., the width direction of the collector). FIG. 1 shows that four spinning nozzles 41a, 41b, 41c and 41d are arranged at intervals along the advancing direction of the collector 6 for convenience of explanation.

The spinning nozzles 41a, 41b, 41c and 41d arranged along the traveling direction of the collector 6 can be arranged, for example, 30-60, or more if necessary, It is possible to increase the rotation speed of the collector 6 and to increase the productivity.

The spinning liquid tank 1 can contain an agitator 2 using a mixing motor 2a as a driving source and is connected to the spinning nozzles 41 to 44 of each row through a metering pump It is connected.

The polymer spinning solution sequentially discharged from the four spinning nozzles 41a, 41b, 41c and 41d is discharged to the ultrafine fibers 5 while passing through the spinning nozzles 41a, 41b, 41c and 41d charged by the high voltage generator. The nanofiber web 7 is formed by sequentially accumulating microfine fibers on a collector 6 of a conveyor type moving at a constant speed. Here, when the spinning solution in which the ion exchange resin particles are further mixed is radiated, a multi-layered nanofiber web composed of nanofibers in which ion exchange resin particles are dispersed can be formed.

FIG. 2 is a flow chart illustrating a process of manufacturing a liquid chemical filter using a sulfonated nanofiber web according to the first embodiment of the present invention. FIG. 3 is a cross- 4A and 4B are conceptual process sectional views for explaining structural characteristics of an example of a multi-layered nanofiber web applied to the first embodiment of the present invention.

Referring to FIG. 2, a spinning solution is prepared by mixing a polymer material and a solvent (S10). Ion exchange resin particles may be further mixed with the spinning solution. The spinning solution is placed in the spinning solution tank 1 of FIG. 1 for electrospinning and electrospinning is carried out to form a multi-layered nanofiber web 7 (S11). When the electrospinning is carried out in a plurality of spinning nozzles, the diameter of at least one spinning nozzle, of the plurality of spinning nozzles, differs from the diameter of the remaining spinning nozzles, the nanofibers of at least one of the multiple layers of laminated nanofibers Layer nanofiber web having a diameter different from the diameter of the nanofiber of the remaining layer is formed.

Thereafter, a sulfonic acid group is introduced into the multi-layer nanofiber web (S12). As shown in FIG. 3, the multi-layer nanofiber web 100 is dipped into a solution 150 in which a sulfonation reaction is performed in which one of concentrated sulfuric acid, fuming sulfuric acid, and chlorosulfonic acid is substituted with a hydrocarbon, It is preferable that a sulfonic acid group is introduced by attaching sulfone groups to the nanofibers and ion exchange resin particles of the web 100. As an optional additional step, a heat treatment process may be performed to improve the stability and durability of the multi-layer nanofiber web 100. The heat treatment process is preferably UV irradiation. Of course, a drying process may also be required prior to the heat treatment process.

As a result, the nanofiber of the multi-layered nanofiber web and the ion exchange resin particle are attached with a sulfonic acid group (-SO ₃ H), and the ion exchange resin particle and the sulfone group cause specific ions Lt; / RTI >

In the present invention, the air electric discharge and the air electric discharge are shown in FIG. 2 and FIG. 6, but the present invention is not limited thereto. The air electric discharge may be applied to any spinning process using electricity, The process may use any one of electrospinning, air-electrospinning (AES), centrifugal electrospinning, flash-electrospinning, and air- All injection processes can be applied.

Referring to FIGS. 4A and 4B, the multi-layer nanofiber web is composed of a nanofiber web laminated in multiple layers. For example, after the first layer of the nanofiber web 101 is formed in the spinning nozzle 41a as shown in FIG. 4A, the spinning nozzle 41b shown in FIG. 4B is coated with the nanofibrous web 101 of the first layer The nanofiber web 101 of the second layer is laminated and formed.

In the present invention, in order to impart various filtering functions of the liquid treatment chemical filter, the diameter of the nanofiber web 101 of the first layer and the diameter of the nanofiber of the nanofiber web 102 of the second layer are designed differently can do. For this purpose, the diameters of the nozzle tips radiated from the spinning nozzles 41a and 41b are designed differently.

Therefore, if the nanofiber diameter of the first layer nanofiber web 101 is designed to be larger than the nanofiber diameter of the second layer nanofiber web 102, the average of the nanofiber web 101 of the first layer The pore size may be larger than the average pore size of the nanofiber web 102 of the second layer. Here, the nanofiber diameter can be a factor that can control the average pore size, but the average pore size does not depend solely on this factor.

On the other hand, suppose that the treated water is passed through the first layer of nanofiber web 101 to the second layer of nanofiber web 102 to perform a filter function. If the average pore size of the nanofiber web 101 of the first layer is relatively larger than the average pore size of the nanofiber web 102 of the second layer, And is filtered as it passes through the fibrous web 101. Particles of small-sized matter contained in the treated water are then filtered in the second layer of nanofiber web 102 having average pores that are relatively smaller than the average pore size. Thus, the liquid treatment chemical filter using the nanofiber web of the present invention can have a multistage filtration function by taking advantage of the structural characteristics of the nanofiber web.

In the present invention, as the diameter of the nanofiber decreases, the average pore and the maximum pore decrease. In addition, as the diameter of the nanofiber decreases, the density increases, so that the basis weight and the average thickness increase, while the air permeability decreases, but the finer pollutants can be filtered and the filtering effect increases.

5 is a schematic view of an electrospinning and electrospray device applied to a second embodiment of the present invention.

The electrospinning and spraying method applied to the present invention is characterized in that high voltage electrostatic force is applied between the spinning nozzles 41 and 43 through which the first and second spinning solutions are radiated and between the spraying nozzle 42 and the collector 6 through which the spinning solution is sprayed The first multi-layered nanofiber web, the ion exchange resin particles, and the second multi-layered nanofiber web are successively firstly radiated, sprayed, and secondly radiated to the collector 6 to form a first multi- It is possible to disperse the ion exchange resin particles.

The injected nanofibers 5 and the injected beads are injected into the collector 6 by spraying the air 4a during the spinning process in the spinning nozzles 41 and 43 and the spinning process in the spinning nozzle 42. [ So that it can be prevented from being blown.

5, the electrospinning and injecting apparatus of the present invention includes a stirrer 2 that uses a mixing motor 2a as a driving source and is connected to spinning nozzles 41 and 43 for supplying a stirred spinning solution And a stirrer 2 which uses a mixing motor 2a as a driving source similar to the first spinning solution tank 1 and which is provided with an injection nozzle And the second spinous liquid tank 1a connected to the spinning nozzle 42. The spinning nozzles 41 and 43 and the spinning nozzle 42 are connected to the high voltage generator.

Here, assuming that the first and second multi-layered nanofiber webs are formed of the nanofibers radiated from the spinning solution composed of the same components (the polymer substance and the solvent), two spinning nozzles 41, 43), or when the components of the spinning solution for forming the first and second multi-layered nanofiber webs are different, the spinning solution of the other component is put in the two spinning solution tanks, And the spinning nozzle '41' is connected to the spinning nozzle '43', and the spinning nozzle '43' is connected to the other spinning solution tank.

The spinning nozzle 40 may be disposed on a conveyor-type grounded collector 6 moving at a constant speed and may be arranged in a plurality of rows spaced along the traveling direction of the collector 6, Of the spinneret.

The first spinning liquid tank 1 is connected to the first and second spinning nozzles 41 and 43 through a metering pump and a transfer tube 3 which are not shown and the second spinning liquid tank 1a is also connected to a metering pump (Not shown) and a delivery pipe (not shown).

The polymer spinning solution sequentially discharged from the spinning nozzles 41 and 43 is discharged to the nanofibers 5 while passing through the spinning nozzles 41 and 43 charged by the high voltage generator, The nanofibers are sequentially laminated on the grounded collector 6 to form a porous nanofiber web.

When the sprayed bead is injected into the first nanofiber web and the sprayed bead reaches the first nanofiber web, most of the solvent is volatilized so that the first nanofiber The ion exchange resin particles are dispersed and settled on the web.

In the present invention, air is injected from the outer periphery of the spinning nozzle when the spinning nozzle is sprayed by the air electrospinning method in which air 4a is sprayed for each spinning nozzle 41 and 43, It is possible to produce a membrane having a higher rigidity.

When a plurality of multi-hole radiation packs are used for mass production, mutual interference occurs and the fibers are blown away and are not collected. As a result, the nanofiber web obtained becomes too bulky and causes radiation trouble .

Therefore, according to the present invention, it is possible to minimize radiation troubles that may occur when air is blown around the spinning nozzles 41 and 43 to fly the fibers.

In the same manner, when air is jetted from the injection nozzle 42, the beads injected into the first multi-layered nanofiber web 7 can be well seated and the beads of the injection solution can be prevented from flying.

A plurality of air injection nozzles (not shown) are provided on the outer circumference of the spinning nozzles 41 and 43 and the injection nozzles 42 used in the present invention. The fibers and the beads of the spray liquid sprayed from the spray nozzle 42 can be guided and integrated. The air pressure of the air injection is set in the range of 0.1 to 0.6 MPa. In this case, when the air pressure is less than 0.1 MPa, it can not contribute to the collection / accumulation. When the air pressure exceeds 0.6 MPa, the cone of the spinning nozzle is hardened, and the needle is closed to cause radiation trouble.

Although the electrospinning and electric spraying apparatus shown in Fig. 5 exemplifies formation of the two-layered nanofiber web 7 by the two spinning nozzles 41 and 43, The spinneret 41 of the previous process and the spinneret 43 of the post-process after the spinneret are formed in a plurality of ways so that the spinneret 42 is sprayed before the spinneret is sprayed. Layer nanofibrous web of the process and the second multi-layered nanofiber web of the (post) process after the spraying liquid is sprayed from the spray nozzle 42 are each passed through a multi-layered nanofiber web in which a plurality of spinning nozzles are arranged in a plurality of rows and a plurality of rows, Layered nanofibrous web composed of an ultra thin film for each layer by applying a hole spinning pack.

Thus, a nanofiber web 7 laminated in two layers in which ion exchange resin particles are dispersed by electrospinning and electrospinning is formed, and then a calendering process for thermally pressing the laminated nanofiber web 2 layers is selected . ≪ / RTI > In the calendering step, a heating press roller (not shown) may be used. In this case, if the lamination temperature is too low, the web becomes too bulky and not rigid, and if it is too high, the web melts and the pores become clogged.

In addition, since the nanofiber web having a multi-layer structure is required to be thermocompression-bonded at a temperature at which the solvent remaining in the web forming the outer surface layer can be completely volatilized, the structure difference of the web There is a difference in degree of filtration, so that surface filtration on the surface layers on both sides and deep filtration on the inner layer are performed.

FIG. 6 is a flow chart of a manufacturing process of a liquid treatment chemical filter using a sulfonated nanofiber web according to a second embodiment of the present invention. FIGS. 7A to 7C are cross- FIG. 2 is a conceptual cross-sectional view illustrating a manufacturing process of a nanofiber web having a plurality of nanofibers.

Preparing a first spinning solution by mixing the polymer material and a solvent, first spinning the first spinning solution to form a first multi-layered nanofiber web, mixing the ion exchange resin particles and the solvent to prepare a solution for dispersion, The ion exchange resin particles are dispersed in the first multi-layered nanofiber web by carrying out a mash-up, the second spinning solution is prepared by mixing the polymer material and the solvent, and the second spinning solution is subjected to the second spinning, Layered nanofiber web on a dispersed first multi-layered nanofiber web and introducing a sulfonic acid group into the first and second multi-layered nanofiber webs to form a liquid-treated chemical filter using a sulfonated nanofiber web .

Referring to FIG. 6, first, a first spinning solution is prepared by mixing a polymer material and a solvent (S100), and a first spinning solution is electrospun to form a first multi-layered nanofiber web (S110). Thereafter, the ion exchange resin particles and the solvent are mixed to prepare a solution for dispersion (S120), and the ion exchange resin particles are dispersed in the first multi-layered nanofiber web (S130). Then, the second spinning solution is prepared by mixing the polymer material and the solvent (S140), and the second spinning solution is subjected to second electrospinning to form a first multilayer nanofiber web in which the ion exchange resin particles are dispersed and a second multilayer nanofiber The web is laminated (S150). Thereafter, sulfonic acid groups are introduced into the laminated first and second multi-layered nanofiber webs (S160), and a heat treatment process is selectively performed (S170).

The liquid processing chemical filter having the nanofibers and the sulfonic acid groups attached to the nanofibers and the ion exchange resin particles is produced.

In this case, when the first spinning solution and the second spinning solution component are the same, the polymer material and the solvent are mixed and put into the stirring tank 1 of FIG. 5 for electrospinning and sprayed from the spraying nozzle 42 The spinning solution of the stirring tank 1 is supplied to the spinneret 41 of the previous process before the spinning solution is sprayed and to the spinning nozzle 43 of the spinning process after the spinning process, When the components of the spinning solution are different, the first spinning solution is put in one stirring tank, the second spinning solution is put in the other stirring tank, and the spinning solution is sprayed to the spinning nozzle 41 So that the first spinning solution is supplied and the second spinning solution is supplied to the spinning nozzle 43 of the (post) spinning process after the spinning solution is injected.

7A to 7C, the first spinning solution is electrospun in the spinning nozzle 41 to form a first nanofibrous web 100 made of nanofibers 110 (FIG. 7A), and the injection nozzles 42 (FIG. 7B). Herein, in the injection nozzle 42, the liquid fraction is injected into a bead (not shown). The liquid is injected into the first nanofiber web 100, 310), most of the solvent is volatilized, and only the ion exchange resin particles 300 are deposited on the first nanofiber web 100. Thereafter, the second spinning solution is electrospun by the spinning nozzle 43 to laminate the second nanofiber web 200 made of the nanofibers 210 in the first nanofiber web 100 (Fig. 7C)

In the present invention, the thickness of the first nanofibrous web 100 and the thickness of the second nanofibrous web 200 may be designed differently in order to impart various filtering functions of the liquid chemical filter, The diameter of the nanofibers 110 of the second nanofibrous web 200 and the diameter of the nanofibers 210 of the second nanofibrous web 200 may be the same or different.

In the second embodiment of the present invention, the fractionating liquid in which the ion exchange resin particles and the solvent are mixed is injected in the bead state from the injection nozzle, and when the injected bead reaches the first nanofiber web, most of the solvent is volatilized do. Therefore, the ion exchange resin particles are segregated and dispersed in various positions of the first nanofiber web in a dispersed state.

Since the beads injected from the injection nozzle contain most of the ion exchange resin particles in a state in which the solvent surrounds the ion exchange resin particles and the solvent is volatilized while descending toward the first nanofiber web, And the bead size adjacent to the first nanofiber web is relatively smaller than the size of the beads originally injected from the injection nozzle. Upon reaching the first nanofiber web, most of the solvent is volatilized and the ion exchange resin particles are deposited and distributed at various locations on the first nanofiber web.

On the other hand, in the second embodiment of the present invention, the ion exchange resin particles are randomly dispersed outside the nanofibers of the first nanofiber web. In the state where the ion exchange resin particles are seated on the first nanofiber web , It is possible that the ion exchange resin particles migrate due to external force and are concentrated in a local region. In this case, in the region where the ion exchange resin particles are not distributed, the treated water that has not been subjected to the chemical filtering passes as it is, and the chemical filtering efficiency is lowered.

Accordingly, in order to minimize the movement of the sprayed ion exchange resin particles, a second nanofiber web for locking to fix the initial position where the ion exchange resin particles sprayed on the first nanofiber web is seated is provided. 1 < / RTI > nanofiber web.

FIG. 8 is a flowchart of a process that can be selectively added to the manufacturing process of the liquid processing chemical filter according to the first and second embodiments of the present invention.

After completion of the multi-layer nanofiber web by the processes of the first and second embodiments, the process of FIG. 8 can be selectively performed. That is, the first and second multi-layered nano-fiber webs are subjected to primary calendering (S200), and the remaining solvent and moisture remaining on the surface of the porous web are controlled to form first and second multi- And dried to control the strength and porosity of the laminated structure of the fibrous web (S210). Here, the primary calendering is to remove the solvent and moisture and to squeeze the laminated structure of the first and second multi-layered nanofiber webs. When the drying is completed, secondary calendering is performed to realize smaller pores and increase the strength (S220). Next, a nonwoven fabric is added to both sides of the laminated structure of the first and second multi-layered nanofiber webs subjected to the second calendering to form a composite material, and then bending is performed (S230). Then, sealing and casing assembly are performed on the folded composite filter media (S240).

Here, when the secondary calendering is completed, the support body can be joined. At this time, the support may be laminated on each of the upper and lower portions of the laminated structure of the multilayer first and second multilayer nanofiber webs, or may be laminated only on either the upper portion or the lower portion of the laminated structure of the first and second multilayer nanofiber webs . For example, FIG. 7 shows that the support 500 is joined to only the lower portion of the laminated structure of the first and second multi-layer nanofiber webs 100 and 200. The support 500 may be a nonwoven fabric or an imitation.

After such a series of processes, a plurality of laminated structures of the first and second multi-layered nanofiber webs in which the nonwoven fabric is laminated can be laminated to form a flat-plate liquid-treated chemical filter, and the first and second multi- The laminated structure of the nanofiber web can be rolled to realize a roll type liquid processing chemical filter.

The embodiments of the present invention described above are not defined as a filter material of a liquid treatment chemical filter but are defined as a liquid treatment chemical filter of an upper concept and are further described as a modularization process selected from various modularization processes, The modularization process is not described in detail.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is clearly understood that the same is by way of illustration and example only and is not to be construed as limited to the embodiments set forth herein. Various changes and modifications may be made by those skilled in the art.

1,1a: Reflective solution tank 6: Collector
7: nanofiber web 41, 41a, 41b, 41c, 41d, 43: spinning nozzle
42: injection nozzle 100,101,102,200: nanofiber web
110, 210: Nano fiber 300: ion exchange resin particle

Claims (20)

delete delete delete delete delete A first multi-layered nanofiber web having micropores laminated with nanofibers obtained by electrospinning a polymer material;
Ion exchange resin particles dispersed in the first multi-layer nanofiber web and positioned outside the nanofibers;
A second multi-layered nanofiber web in which nanofibers obtained by electrospinning of a polymer material are laminated on a first multi-layered nanofiber web in which the ion-exchange resin particles are dispersed, for preventing movement of the ion-exchange resin particles; And
And a sulfonic acid group introduced into the first and second multi-layered nanofiber webs. 7. The method of claim 6, wherein a support is formed on either the first multi-layer nanofiber web, the second multi-layer nanofiber web, or both the first and second multi-layer nanofiber webs. Liquid treatment chemical filter using nanofiber web. [Claim 8] The method of claim 7, wherein the liquid treatment chemical filter comprises a plate-like structure in which a plurality of the first and second multi-layered nanofiber webs are laminated with the support, Characterized in that the polymer is a roll-type structure of a liquid-treated chemical filter using a sulfonated nanofiber web. 7. The liquid treatment chemical filter according to claim 6, wherein the ion exchange resin particles are cation exchange resin particles or anion exchange resin particles. The liquid treatment chemical filter according to claim 6, wherein the thickness of the first multi-layer nanofiber web and the thickness of the second multi-layer nanofiber web are different. 7. The liquid treatment chemical filter according to claim 6, wherein the diameter of the nanofiber of the first multi-layer nanofiber web and the diameter of the nanofiber of the second multi-layer nanofiber web are the same or different. . 7. The liquid treatment chemical filter of claim 6, wherein the average pore size of the first multi-layer nanofiber web is greater than the average pore size of the second multi-layer nanofiber web. delete delete delete Preparing a first spinning solution by mixing the polymer material and a solvent;
Forming a first multilayer nanofiber web by first electrospinning the first spinning solution;
Mixing the ion exchange resin particles with a solvent to prepare a solution for fractionation;
Dispersing the ion exchange resin particles in the first multi-layered nanofiber web by electrospinning the dispersion with the first multi-layered nanofiber web;
Mixing a polymer material and a solvent to prepare a second spinning solution;
Layering the nanofibers obtained by the second electrospinning of the second spinning solution onto a first multi-layer nanofiber web in which the ion exchange resin particles are dispersed to form a second multi-layer nanofiber web; And
And introducing a sulfonic acid group into the multi-layered nanofiber web. ≪ RTI ID = 0.0 > 8. < / RTI > 17. The method of claim 16, wherein air is sprayed to prevent the ejected nanofibers and injected beads from blowing during the first and second electrospinning and the electrospinning, (METHOD FOR MANUFACTURING LIQUID - PROCESSED. 17. The method of claim 16, wherein the size of the beads adjacent to the first multi-layer nanofiber web is smaller than the size of the beads initially sprayed. 17. The method of claim 16, wherein the nanofiber diameter of the first multi-layer nanofiber web and the nanofiber diameter of the second multi-layer nanofiber web are the same or different. ≪ / RTI > The sulfonated nanofiber web according to any one of claims 16 to 19, further comprising a heat treatment step for improving the stability and durability of the nanofiber web after the step of introducing the sulfonic acid group Method of manufacturing a liquid treatment chemical filter.

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