KR20220027673A - Spiral wound type ultrafiltration module for manufacturing ultrapure water and System of manufacturing ultrapure water - Google Patents

Abstract

The present invention relates to an ultrafiltration module and an ultrapure water cleaning system using the same, and more specifically, to an ultrafiltration module and an ultrapure water cleaning system using the same, wherein the ultrafiltration module is manufactured by winding a flat membrane instead of a hollow fiber membrane, and ultrapure water is cleaned (or manufactured) by using the same, thereby reducing cleaning time and securing a stable particle removal rate against changes in the operating environment of the ultrafiltration module.

Description

Spiral wound type ultrafiltration module for manufacturing ultrapure water and System of manufacturing ultrapure water

The present invention relates to a spiral wound type ultrafiltration module, and relates to a flat membrane spiral wound type ultrafiltration module capable of improving problems caused by application of a hollow fiber type ultrafiltration module during the production of existing ultrapure water, and to an ultrapure water manufacturing system using the same.

At the end of the ultrapure water production device, a micro-ion removal device (EDI) and a hollow fiber type ultrafiltration module for the purpose of removing microbe-derived microparticles are installed. The hollow fiber module has a higher specific surface area than a flat membrane or a pleated membrane, so the filling amount is relatively low, but the water permeability per module is excellent. The biggest advantage is that the ultrafiltration module using the hollow fiber membrane is superior to other types of modules even at the non-membrane filtration flow rate (L/m ² .hr.bar) due to the above characteristics.

As the demand for the quality of ultrapure water becomes stricter, the demand for the ultrafiltration membrane device is also getting stricter. In addition, there is also a demand for short-term start-up of the ultrapure water production apparatus, and a method of pre-cleaning the ultrafiltration membrane apparatus has been proposed. Japanese Patent Laid-Open No. 2004-66015 discloses cleaning the ultrafiltration module installed in the ultrapure water production device in a dedicated cleaning device. The contents performed by repeating a cleaning cycle consisting of an immersion process and a drainage process of ultrapure water are disclosed.

Recent advances in semiconductor design and manufacturing are driving the development of increasingly smaller and more powerful devices. The smaller dimensions used in such structures make such structures increasingly sensitive to the presence of smaller particles present in the processing fluid used to fabricate the device, for example ultrapure water (UPW). And, ultra-nanoparticles of 20 nm or less can significantly affect the yield of certain semiconductor devices. The detection and removal of such small particles is a difficult problem to solve, and it is important to remove TOC (total organic carbon) and particulates generated from the module itself before installing the module in the ultrapure water production device. The conventional ultrafiltration membrane device using a hollow fiber membrane has a high TOC elution amount when cleaning due to the amount of adhesive applied to the potting of the ultrafiltration module and the potting thickness. This increases the cleaning time before installing the module, which in turn increases the cleaning cost. In addition, TOC is eluted even when producing ultrapure water by the installed module, which may cause a problem of lowering the quality of ultrapure water.

The hollow fiber type ultrafiltration membrane has a relatively low membrane filling rate in the module compared to the flat membrane, so there is a relatively large amount of free space between the hollow fiber membranes. This causes the flow of the hollow fiber membrane by changes in external pressure, fluid flow, temperature, etc., and when continuous thermal and mechanical impact is applied to the hollow fiber membrane, the durability of the hollow fiber membrane is lowered. This has a problem in that the removal performance of the membrane module is eventually lowered.

Korea Patent Publication No. 1998-018343 (published on June 5, 1998)

The present invention provides an ultrafiltration module to which a flat membrane spiral wound type ultrafiltration membrane (or filter module) is applied rather than a hollow fiber type ultrafiltration membrane as an ultrafiltration module that stably performs particle removal ability, which is the original purpose of final UF (ultrafiltration), against external changes, and an ultrafiltration module using the same An object of the present invention is to provide a system for producing ultrapure water using

In order to solve the above problems, the present invention relates to a spiral wound type ultrafiltration module, comprising: a housing; and a spiral wound filter module packed in the housing, wherein when the packing density of the spiral wound filter module is measured based on Equation 1 below, the packing density may be 80 to 99%. .

[Equation 1]

packing density = (A - B)/A × 100

In Equation 1, A is the inner volume of the unit cell (Inner Volume of Unit Cell), B is the volume of the packed water (Volume of Packing Water).

As a preferred embodiment of the present invention, the spiral wound ultrafiltration module of the present invention is cleaned with ultrapure water having a total organic carbon (TOC) of 1 ppb or less and a specific resistance of 18 MΩ or more, but the TOC concentration of the filtered water is within 18 hours of the module cleaning time It may be 1 ppb or less.

As a preferred embodiment of the present invention, the spiral wound type ultrafiltration module of the present invention includes a perforated tube having at least one inlet hole; a cylindrical filter body in which a membrane sheet and a sheet of a permeate flow passage are sequentially stacked in a single layer or in multiple layers, and the cylindrical filter body is wound around the outer surface of the perforated tube in a spiral wound shape; and a bonding unit for bonding the lower membrane sheet to the permeate passage sheet and the permeate passage sheet to the upper membrane sheet.

As a preferred embodiment of the present invention, the joint portion includes a pair of joint extension lines extending in parallel along both sides of the edge of at least one of the membrane sheet and the permeate flow passage sheet, and a pair of joint extension lines facing each other It may include a bending line bent in a direction opposite to each other so as to be close to the inlet hole from the start end of a joint connection line connecting between the end ends of the perforated pipe and a pair of joint extension lines corresponding to the perforated pipe.

As a preferred embodiment of the present invention, the bending line may be provided in a straight line parallel to the perforated tube.

As a preferred embodiment of the present invention, the bending line may be provided to be inclined at a certain angle in a direction that approaches or moves away from the perforated tube.

As a preferred embodiment of the present invention, it may include a fusion portion for temporarily fixing the sheet laminate at a position between the outer edge of the cylindrical filter body and the bonding extension line.

As a preferred embodiment of the present invention, the outer surfaces of both ends of the perforated tube may include at least one groove in which a portion of the adhesive flowing out from the joint interposed between the sheet laminates is accommodated.

As a preferred embodiment of the present invention, the groove may be provided at a position corresponding to between the outer edge of the cylindrical filter body and the joint extension line.

As a preferred embodiment of the present invention, the groove may include an absorbent member for absorbing a portion of the adhesive.

As a preferred embodiment of the present invention, the bonding portion may include a polyepoxy adhesive resin.

As a preferred embodiment of the present invention, the membrane sheet may include a polysulfone flat membrane.

As a preferred embodiment of the present invention, the polysulfone flat membrane is prepared from a polymer solution containing a sulfonated polysulfone-based polymer, a polysulfone-based polymer, and a solvent, and the polysulfone-based polymer is a polysulfone polymer, polyether It may include at least one selected from a sulfone polymer and a polyallyl ether sulfone polymer.

As a preferred embodiment of the present invention, the permeate passage sheet may include a tricot filter fabric.

As a preferred embodiment of the present invention, in the multi-layered sheet laminate, a mesh sheet is placed between the membrane sheets of the laminated sheet laminated body adjacent to each other.

Another object of the present invention is to provide an ultrapure water production system using the spiral wound type ultrafiltration module described above.

The spiral wound ultrafiltration module of the present invention can use a small amount of adhesive to minimize or prevent the elution amount of the adhesive, reduce the rinse down time of the semiconductor application module, and minimize or eliminate empty space in the housing. Stable operation is possible with respect to changes in conditions (pressure, flow rate), so it can have removal efficiency for TCO and particles. In addition, it is easy to install and replace, the price per module is low, and the module stacking is possible, so it is possible to save space during installation and reduce equipment manufacturing costs.

1A and 1B are a perspective view and a plan view illustrating a preparation step in a process for manufacturing a spiral wound filter module according to an embodiment of the present invention.
2A and 2B are a perspective view and a plan view illustrating a joint forming step in a process for manufacturing a spiral wound filter module according to an embodiment of the present invention.
3A and 3B are perspective and plan views illustrating a process of laminating filter materials while forming a joint in a process of manufacturing a spiral wound filter module according to an embodiment of the present invention.
4 is a perspective view illustrating a process of cutting a wound filter body in a process of manufacturing a spiral wound filter module according to an embodiment of the present invention.
5A and 5B are a perspective view and a plan view illustrating another form of a junction part in a spiral wound filter module according to an embodiment of the present invention.
6A and 6B are a perspective view and a plan view illustrating an embodiment to which a fusion part is applied in a spiral wound filter module according to an embodiment of the present invention.
7 is a perspective view illustrating an embodiment in which an adhesive receiving groove is applied in a spiral wound filter module according to an embodiment of the present invention.
8 is a result of measuring the number of particles in produced water according to the flux of Example 1 and Comparative Example 1 carried out in Experimental Example 1. FIG.
9 is a result of measuring the flux according to the differential pressure of incoming and produced water in Example 1 and Comparative Examples 1 and 2 carried out in Experimental Example 1. FIG.

Hereinafter, preferred embodiments in which those of ordinary skill in the art to which the present invention pertains can easily practice the present invention will be described in detail with reference to the accompanying drawings. However, in the detailed description of the structural principle of the preferred embodiment of the present invention, if it is determined that a detailed description of a related well-known function or configuration may unnecessarily obscure the gist of the present invention, the detailed description thereof will be omitted.

In addition, the same reference numerals are used throughout the drawings for parts having similar functions and functions.

In addition, throughout the specification, when a part is 'connected' with another part, it is not only 'directly connected' but also 'indirectly connected' with another element interposed therebetween. include In addition, 'including' a certain component does not exclude other components unless otherwise stated, but means that other components may be further included.

The spiral wound type ultrafiltration module of the present invention includes a housing; and a spiral wound filter module packed in the housing, and a preferred embodiment of the method for manufacturing the spiral wound filter module is as follows.

The size and shape of the housing (or pressure case) may not be limited within an acceptable range for the spiral wound filter module, but preferably, since the filter module is wound in a spiral wound type, the shape of the housing is It can be cylindrical. However, the shape of the housing is not limited thereto. The material of the housing may be used without limitation, a housing made of a material commonly used in the ultrafiltration module in the art.

The spiral wound filter module can be manufactured by performing a process including a perforated pipe preparation step (S1), a junction forming step (S2), a lamination step (S3), a winding step (S4), and a cutting step (S5).

The preparation step (S1) is to prepare at least one perforated tube 10 and a membrane sheet 21, and to arrange the perforated tube at one end of the membrane sheet 21, as shown in FIGS. 1A and 1B. .

The perforated pipe 10 may be formed of a hollow pipe member of a certain length which is opened at one or both ends of both ends, and is formed through at least one inlet hole 12 through which production water is introduced in the middle of the length.

The perforated tube 10 has been illustrated and described as being disposed at one end of the membrane sheet, but is not limited thereto, and may be prepared by being disposed at one end of the permeate passage sheet.

The membrane sheet 21 may be at least one selected from a polyamide-based separator, a polyimide-based separator, a polysulfone-based separator, and a polyether sulfone-based separator, preferably a polysulfone-based separator, more preferably a polysulfone-based separator It may be a flat membrane, and the permeate channel sheet 22 may include a tricot filter fabric (or tricot paper). Hereinafter, the membrane sheet and the permeate passage sheet of the present invention will be described in more detail.

The sheet laminate 20 comprising the membrane sheet 21 and the permeate passage sheet 22 is laminated and laminated through a joint to be described later in a multi-layered state and wound in a roll form on the outer surface of the perforated tube. it will be recommended At this time, the permeate flow passage sheet 22 is disposed between two membrane sheets, that is, the permeate flow passage sheet is disposed between the lower membrane sheet and the upper membrane sheet.

As shown in FIGS. 2A and 2B, in the bonding part forming step (S2), a pair of left and right bonding extension lines having a predetermined width by applying a bonding agent linearly along both edges of one side of the membrane sheet 21 (31) is formed, and a bonding agent is applied linearly to connect each end end of a pair of bonding extension lines (31) facing each other to form a bonding connection line (32).

Then, the pair of joint extension lines 31, the pair of joint extension lines 31, are bent in a direction opposite to each other from each starting end of the pair of joint extension lines corresponding to the perforated pipe 10 to form a bent line 33 extending a certain length A joint portion 30 composed of a connecting line and a bending line 33 is formed.

In this case, the junction part 30 interposed between the membrane sheet 21 and the permeate passage sheet 22 and joining them is formed by the pair of junction extension lines 31, junction connection lines 32 and bending. By forming an approximately “C”-shaped junction line that is opened toward the perforated tube by the line 33 , the permeated water passing through the membrane sheet 21 forms a permeated water passage flowing into the inlet of the perforated tube.

In the process of forming such a bonding part on one surface of the membrane sheet, the bonding agent applicator (not shown) is disposed so as to correspond to one side of the membrane sheet spread on the bottom surface, and the bonding agent applicator is applied at a constant speed in the longitudinal direction of the sheet. By discharging the binder linearly while moving, the bonding extension line is formed by the bonding agent discharged from the discharge port of the bonding agent applicator facing the membrane sheet, and moving in the longitudinal direction in the moved or stopped binder applicator A splicing connection line connecting between the end ends of a pair of splicing extension lines is formed by the discharge port, and bent lines bent in opposite directions are formed at each end end of the pair of splicing extension lines.

The lamination step (S3) is, as shown in FIGS. 3A and 3B, the membrane sheet 21 and the permeate passage sheet ( 22) is laminated to form a bonded sheet laminate 20, and at the same time, another membrane sheet or a sheet is placed on the lower sheet laminate 20 through a permeate flow passage to form a junction to form the sheet laminate 20 By repeating the above process, the sheet laminate can be laminated in multiple layers.

In this case, it is preferable that the end portions of the sheet laminate facing the perforated tube are laminated to form a step shape rather than being laminated in a vertical direction.

And, in the multi-layered sheet laminate, a mesh sheet, which is a mesh sheet, is placed to form a flow path through which raw water is supplied between the membrane sheets of the sheet laminate stacked adjacent to each other.

Here, the membrane sheet 21 may be formed of a filter material in which a mesh sheet, which is a raw water passage material, is inserted between the sheet materials folded in half in the middle to form a flow path through which raw water is introduced and concentrated water is discharged.

In the winding step (S4), as shown in FIGS. 4A and 4B , a driving shaft of a winding chuck (not shown), which is a rotational driving means, is connected to both open ends of the perforated tube 10 .

Then, by rotating the perforated tube 10 in one direction by the winding chuck, the sheet laminate 20 is wound on the outer surface of the perforated tube 10 in the form of a roll, and a cylindrical filter body 40 having the perforated tube in the center of the body ) to form

Here, in the process of winding the cylindrical filter body 40, the adhesive of the bonding part 30 that bonds between the membrane sheet of the sheet laminate 20 and the sheet through the permeate flow path is not completely cured but is in a semi-cured or reactive solid state. Therefore, it is spread by the external force generated during winding between the laminated sheets.

At this time, the bending line 33 of the bonding portion 30 is bent in a direction opposite to each other from the start end of the bonding extension line, so that the adhesive flows out to the short side of the cylindrical filter body by an external force generated during winding. Since it is applied to relatively increase the amount of adhesive applied per unit area at the start end of the joint close to the outer diameter of the perforated pipe in consideration of the external leakage, the adhesive applied at the start of the joint close to the outer diameter of the perforated pipe is maintained It is possible to preserve the amount and prevent the occurrence of holes on the short side of the cylindrical filter body due to excessive leakage of adhesive while suppressing as much as possible.

In addition, the bending line 33 is applied to extend inwardly in a direction opposite to each other from the start end of the bonding extension line 31, so that it does not spread to the short side of the cylindrical filter body 40 by an external force generated during winding. Since it spreads inward, the occurrence of holes on the short side of the cylindrical filter body due to excessive outflow of the adhesive as the adhesive at the joint excessively flows out to the outside of the short side of the cylindrical filter body can be prevented while suppressing as much as possible.

As shown in FIGS. 2A and 2B, the bent line 33 is bent at an approximately right angle to the start end of the joint extension line and extended to a predetermined length in parallel with the perforated tube, but is not limited thereto. As shown in 5a and 5b, the perforated pipe 10 is provided inclined at a certain angle (θ) in a direction away or close to the side to increase the amount of adhesive applied at the start end of the joint adjacent to the perforated pipe 10. can

The extension length (L) of the bending line 33 may be set to 0.1 ~ 50mm to apply the adhesive, more preferably 5 ~ 20mm may be set to apply the adhesive.

A certain angle (θ) of the bent line formed to be inclined away from or close to the perforated pipe 10 side is illustrated and described as being formed as an obtuse angle greater than a right angle with respect to the junction extension line, but is not limited thereto, and an acute angle smaller than a right angle can be formed with

On the other hand, in order to prevent excessive leakage of the adhesive at the joint adjacent to the outer diameter of the perforated tube when the cylindrical filter body is wound by the winding process of the sheet laminate, the membrane sheet and the permeate passage sheet are welded to each other. It may be provided with a recess 15 to limit the position of the fusion portion (F) to be temporarily fixed or to temporarily accommodate the adhesive during winding at both ends of the perforated tube.

That is, in the lamination step, the fusion part (F) for partially welding and temporarily fixing one edge of the membrane sheet 21 corresponding to the perforated tube and one edge of the permeate passage sheet 22 is shown in FIGS. 6A and 6B . As shown, it is preferable to be partially formed at a position corresponding to between the outer edge of the cylindrical filter body and the joint extension line.

Accordingly, in the process of winding the sheet laminate 20 to form the cylindrical filter body 40, one side edge of the membrane sheet 21 and one side edge of the permeate passage sheet 22 are partially closed Since the fusion part (F) to be welded and temporarily fixed is arranged close to the outer diameter of the perforated tube and located outside the joint extension line, the adhesive is applied from the vicinity of the outer diameter of the perforated tube to the short side of the cylindrical filter body by the external force generated during winding. It is possible to reduce the amount of outflow of the adhesive by the fusion portion (F) arranged in the outflow path, and to increase the amount of remaining adhesive in the vicinity of the outer diameter of the perforated pipe.

The fusion portion F may partially fusion-bond one edge of the permeate flow passage sheet 22 stacked on the membrane sheet 21 and one edge of the permeate flow passage sheet stacked thereon to temporarily fix them.

In addition, the external force generated during winding on the outer surfaces of both ends of the perforated pipe (10)

As shown in FIG. 7, the recess 15 in which a part of the adhesive of the bending line 33 compressed by the pressure is temporarily accommodated is located between the outer edge of the cylindrical filter body and the joint extension line. It may be provided in the form of an annular groove recessed in the outer surface of the perforated tube.

The recess 15 may include at least one absorbing member 15a, such as a sponge, which is inserted and disposed to absorb the liquid adhesive temporarily accommodated during winding.

Accordingly, in the process of winding the sheet stacked body 20 to form the cylindrical filter body 40, external force generated during winding is provided in the grooves 15 that are recessed in the form of annular rings on the outer surfaces of both ends of the perforated tube. Since the adhesive flowing out from the vicinity of the outer diameter of the perforated tube to the short side of the cylindrical filter body is temporarily accommodated by the groove 15, the amount of outflow of the adhesive can be reduced or prevented by the groove 15, and the adhesive remains in the vicinity of the outer diameter of the perforated tube. retention can be increased.

In the cutting step (S5), as shown in FIGS. 5A and 6A, a portion of both ends of the cylindrical filter body 40 is cut by a cut-off wheel (not shown) disposed in a one-to-one correspondence with the joint extension line of the joint portion. By separating and removing the cut material 50, the sheet laminate 20 in which the permeate flow passage sheet and the membrane sheet are bonded through the junction portion are sequentially stacked on the outer surface of the perforated tube 10 located in the center of the body. To manufacture a spiral wound filter module 100 in which a multi-layered sheet laminate is wound in the form of a roll.

Here, the cut material 50 includes a fusion portion (F) for temporarily fixing the membrane sheet and the permeate passage sheet by fusion or a groove 15 in which the adhesive of the joint portion is temporarily accommodated, and separated together with the fusion portion or groove. will be removed

The operation of cutting a portion of both ends of the cylindrical filter body 40 by rotational driving of the cut-off wheel may be performed while rotating the cylindrical filter body in the opposite direction to the rotation direction of the cut-off wheel by the winding chuck, but is limited thereto. This is not the case, and it can be performed by rotating the cut-off wheel in a state where the cylindrical filter body is stopped.

Hereinafter, each of the membrane sheet, the permeate flow passage sheet, and the mesh sheet used for manufacturing the spiral wound type filter module of the spiral wound type ultrafiltration module of the present invention will be described.

[Membrane Sheet]

The membrane sheet 21 used for manufacturing the spiral wound filter module may be at least one selected from a polyamide-based separator, a polyimide-based separator, a polysulfone-based separator, and a polyether sulfone-based separator, preferably a polysulfone-based separator , more preferably a polysulfone-based flat membrane.

In addition, as the polysulfone-based flat membrane, a general polysulfone-based flat membrane used in the art may be used, preferably for water treatment prepared with a polymer solution containing a polysulfone-based polymer, a sulfonated polysulfone-based polymer, and a solvent. You can use flat screens.

Among the components of the polymer solution, the polysulfone-based polymer may include 8 to 20 wt%, preferably 10 to 20 wt%.

And, among the components of the polymer solution, the sulfonated polysulfone-based polymer serves to impart hydrophilicity to the polysulfone polymer, and a sulfonated polysulfone-based polymer represented by the following Chemical Formula 1 may be used, and the entire polymer solution It may contain 1 to 20% by weight, preferably 3 to 18% by weight, more preferably 5 to 15% by weight of the weight. At this time, if the content of the sulfonated polysulfone polymer is less than 1% by weight, the stain resistance and hydrophilic effect of the polysulfone-based membrane are insignificant, and if it exceeds 20% by weight, the strength and physical properties of the membrane are reduced, and the permeability is decreased. There may be a problem.

[Formula 1]

In Formula 1, m/(n+m) is 0.6 to 0.9, and x is 50 to 1000. At this time, if m/(n+m) is less than 0.6, the hydrophilic property of the membrane is weak, so that the stain resistance improvement is insufficient. In addition, x is 50 to 1000, and the weight average molecular weight of the sulfonated polysulfone-based polymer is 50,000 or more, more preferably 50,000 to 1,000,000, more preferably 50,000 to 300,000.

Among the polymer solution components, the solvent may be a polysulfone polymer or a sulfonated polysulfone polymer having high solubility, and preferred examples include N-methyl-2-pyrrolidone, dimethylformamide, dimethylsulfoxide and One or more selected from among dimethylacetamide may be used, but the present invention is not limited thereto.

In addition, the polymer solution may further include a hydrophilic pore control agent for pore control in addition to the polysulfone polymer, the sulfonated polysulfone polymer and the solvent, and may be used as long as it is well mixed with the solvent, but more preferably polyvinyl It may include at least one selected from pyrrolidone, polyethylene glycol, and silica, and more preferably polyvinylpyrrolidone having a weight average molecular weight of 10,000 to 100,000 may be used as a hydrophilic pore control agent. When using the hydrophilic pore controlling agent, the amount used is 5 to 20 wt% of the total weight of the polymer solution, preferably 5 to 15 wt%, and in this case, if the amount is less than 1 wt%, the effect of the hydrophilic pore controlling agent is insignificant If it exceeds 20% by weight, there may be a problem in that the mechanical properties of the membrane are rather lowered.

When explaining an example of manufacturing a polysulfone-based flat membrane using the above-described polymer solution, a first step of forming a membrane by casting the polymer solution on a support; a second step of forming pores in the upper layer of the membrane by spraying air maintained at a temperature of 20 to 60° C. and a humidity of 30 to 80% in the formed membrane; and after the step, a third step of peeling the membrane from the support by immersing it in a coagulation bath to obtain a polysulfone-based flat membrane.

In addition, a post-process of forming pores by immersing the exfoliated film, which has been subjected to step 3, in a water washing tank to extract the remaining solvent components contained in the membrane matrix; and/or a drying process; may be further performed.

[Permeable water passage sheet]

The permeate flow passage sheet 22 used for manufacturing the spiral wound filter module may include a tricot filter fabric (or tricot paper).

The tricot filter fabric may use a general tricot filter fabric for water treatment membranes used in the art, preferably a tricot filter fabric made of polyethylene terephthalate (PET) yarn or a tricot filter fabric made of a core-sheath composite yarn can be used

The tricot filter fabric made of the core-sheath-type composite yarn is a step 1 of manufacturing a core-sheath composite yarn by composite spinning a PET resin and a polyester resin; The antimony reduced tricot filter fabric prepared by performing a process comprising; a second step of preparing a tricot filter fabric with the core-sheath composite yarn and a third step of eluting and removing antimony from the tricot filter fabric can be used.

The core-sheath composite yarn of step 1 is not limited as long as it is a method for manufacturing the conventional composite yarn, preferably, it is prepared through composite spinning, and more preferably, it can be prepared through melt spinning.

The core-sheath composite yarn can be prepared by melt-spinning the resin for the deep part and the resin for the sheath part, which are prepared by performing a polymerization reaction of an acid component and an alcohol component under a catalyst containing antimony trioxide.

Specifically, the PET resin may be a resin for the deep part, and the resin for the deep part is at 200 to 300°C, preferably at 230 to 270°C, terephthalic acid and 1,2-ethanediol in a molar ratio of 1:1 to 2 to prepare a first mixture by esterification by mixing in a molar ratio of 1: 1.1 to 1.9, and 0.01 to 0.05 of a catalyst containing antimony trioxide with respect to 100 parts by weight of the first mixture It can be prepared by adding parts by weight, preferably 0.02 to 0.04 parts by weight, and performing the step of preparing the resin by polycondensation at 230 to 320°C, preferably at 260 to 305°C. If the temperature in the step of preparing the first mixture is less than 200° C., the heat of reaction between the first mixture and the catalyst is insufficient, so that the polycondensation reaction cannot occur or a low molecular weight polycondensate is formed so that the strength is low and fiberization is difficult. If the temperature exceeds 300°C, decomposition of the polycondensate occurs due to high reaction heat, making it difficult to secure a target high molecular weight polycondensate, or diethylene glycol and various A problem in that the strength of the polycondensate formed by the generation of dimer-type side reactants is lowered and yellowing is generated may occur. In addition, if the molar ratio of terephthalic acid and 1,2-ethanediol is less than 1:1, it may be difficult to prepare a target high molecular weight polycondensate or to make fiberization of the prepared polycondensate difficult, and the molar ratio is 1 : If it exceeds 2, excessive by-products may be generated, which may lead to thread trimming and increase in pack pressure in the spinning process due to residual unreacted substances, which may significantly reduce spinning workability.

In addition, if the catalyst input in the step of preparing the resin for the first layer is less than 0.01 parts by weight based on 100 parts by weight of the first mixture, it may be difficult to form the target high molecular weight polycondensate, and 0.05 parts by weight If it exceeds, the whiteness of the formed polycondensate is low, and it may act as a foreign material in the spinning process, causing a problem that causes yarn breakage. In addition, if the temperature at which the polycondensation reaction is performed is less than 230 ° C, a problem may occur that the condensation reaction does not occur at a temperature lower than the melting point of the resin for the deep part, and if the temperature exceeds 320 ° C, it is actually a decomposition reaction due to high temperature It is difficult to secure a high molecular weight resin, and carbonization of the resin may occur during the reaction due to high temperature.

And, the polyester resin may be a resin for the first layer, the resin for the first layer is at 200 ~ 300 ℃, preferably at 230 ~ 270 ℃, the acid component and the alcohol component in a molar ratio of 1: 0.8 ~ 2.2, Preferably 1: 1 to preparing a second mixture by esterification by mixing in a molar ratio of 1 to 2, and 0.01 to 0.05 parts by weight of a catalyst containing antimony trioxide based on 100 parts by weight of the second mixture , preferably 0.02 to 0.04 parts by weight, at 230 to 320 ° C., preferably at 260 to 305 ° C. It can be prepared by performing the step of preparing the resin for the first layer by a polycondensation reaction. If the temperature at which the second mixture is prepared is less than 200° C., the heat of reaction with the mixture and the catalyst is insufficient, so that the polycondensation reaction cannot occur or a low molecular weight polycondensate is formed, resulting in low strength and difficult fiberization. When the temperature exceeds 300°C, decomposition of the polycondensate occurs due to high heat of reaction, making it difficult to secure a target high molecular weight polycondensate, or generation of diethylene glycol and various dimer side-reactants generated due to high heat of condensation other than the decomposition reaction. As a result, the strength of the polycondensate formed as a result is lowered and a problem of yellowing may occur. In addition, if the molar ratio of the acid component and the alcohol component is less than 1: 0.8, it may be difficult to prepare a target high molecular weight polycondensate or to make fiberization of the prepared polycondensate difficult, and the molar ratio exceeds 1: 2.2 If the by-products are excessively generated, there may be a problem that the spinning workability may be remarkably deteriorated by inducing trimming and an increase in the pack pressure in the spinning process due to residual unreacted substances. In addition, if the catalyst input in the step of preparing the resin for the first layer part is less than 0.01 parts by weight based on 100 parts by weight of the second mixture, it may be difficult to form the target high molecular weight polycondensate, and 0.05 parts by weight If it exceeds, the whiteness of the formed polycondensate is low, and it may act as a foreign material in the spinning process, causing a problem that causes yarn breakage. In addition, if the temperature at which the polycondensation reaction is performed is less than 230 ° C, the resin for the deep part does not melt, and a problem that the condensation reaction does not occur may occur, and if the temperature exceeds 320 ° C, the resin burns out, or the condensation reaction Problems may arise that do not occur.

Meanwhile, the acid component may include at least one selected from terephthalic acid and isophthalic acid, and the alcohol component may include 1,2-ethanediol and isopropanol.

Next, the step of preparing the tricot filter fabric in the second step is not limited as long as it is a method for conventionally manufacturing the tricot filter fabric, and preferably, the dough prepared by knitting the core component and the sheath component in a conventional method is used. It can be manufactured by performing pretreatment at 90°C to 110°C for 25 to 35 minutes with a batch-type preprocessor to remove impurities, and heat-treating it in a heat tender at 180°C to 200°C at a speed of 15 to 26 m/s.

Next, three steps of eluting and removing antimony from the tricot filter fabric will be described.

Step 3 is a 3-1 step of heat-treating the tricot filter fabric; and 3-2 steps of impregnating the tricot filter fabric in the mixed solution.

In step 3-1, the tricot filter fabric may be heat-treated at 150 to 230 °C, preferably at 160 to 210 °C for 10 to 25 minutes, preferably for 13 to 20 minutes. If the heat treatment temperature is less than 150 ℃, the mechanical strength of the formed trigot filter fabric may be lowered, which may cause difficulties in expressing the desired function. If the temperature exceeds 200 ℃, energy efficiency and economic feasibility are not good, and due to excessive heat As long as the fabric is damaged, problems can arise. In addition, if the heat treatment time is less than 10 minutes, the mechanical strength of the formed tricot filter fabric may be lowered, so that it may be difficult to express the desired function, and if the time exceeds 25 minutes, the problem of poor energy efficiency and economic efficiency can occur

In addition, the mixed solution of step 3-2 may include preparing a mixed solution containing at least one selected from calcium chloride (CaCl ₂ ) and nitric acid (HNO ₃ ) and a solvent, preferably nitric acid and a solvent. .

When calcium chloride is included in the mixed solution, the impregnation of step 3-2 may be performed at 80 to 120 ° C., preferably at 90 to 110 ° C. for 20 to 28 hours, preferably for 22 to 26 hours, but the Considering the long time required and the economical aspect, it is preferable to impregnate in a mixed solution containing nitric acid. When nitric acid is included in the impregnation solution, it may be carried out at 20 to 30° C., preferably at 23 to 28° C. for 18 to 60 minutes, preferably for 20 to 50 minutes.

On the other hand, the nitric acid can be used without limitation as long as it does not damage the fibers and has an excessive concentration of nitric acid, preferably 0.1 to 5.0N nitric acid, more preferably 0.3 to 3.0N nitric acid, and more Preferably, it may be 0.5 to 1.0 N nitric acid. If the concentration of nitric acid is less than 0.1 N, there may be a problem that the antimony removal efficiency is lowered, and if the concentration of nitric acid exceeds 5.0 N, the antimony removal efficiency may be increased, but the strength may be lowered due to damage to the fabric and , it may cause a problem in that it is not easy to remove the residual nitric acid remaining on the fabric.

On the other hand, the residual solution remaining on the fabric in the high-pressure water washing process during the total inspection may be removed. Specifically, the mixed solution partially remaining on the surface of the tricot filter fabric in the high-pressure water washing process may be removed, but is not limited thereto.

The antimony reduction tricot filter fabric described above may have an antimony reduction rate of 90% or more, preferably 92% or more, and more preferably 94% or more when measured based on Equation 2 below.

[Equation 2]

[Mesh Sheet]

The mesh sheet used for the spiral wound filter module serves as an inner and/or outer spacer, and a general mesh sheet used for manufacturing the ultrafiltration module may be used, and preferably, the mesh sheet is arranged in parallel with a predetermined interval. a plurality of first yarns being; And it is characterized in that a plurality of second yarns cross each other at a predetermined angle (θ), and unlike a conventional mesh sheet that forms a linear fluid flow, it is possible to form a three-dimensional fluid flow. The three-dimensional fluid flow may include a linear fluid flow and a fluid flow that detours to a three-dimensional space existing in the mesh sheet when the linear fluid flow is hindered by counter pressure.

The first yarn and the second yarn may be made of any one selected from polyethylene, polypropylene, polyethylene terephthalate, polyester, nylon, or a copolymer thereof, and the material cost is lower than that of the conventional tricot, so that the filter module for water treatment Manufacturing cost can be lowered.

The thickness of the mesh sheet may be 0.2 ~ 0.6 mm, more preferably 0.25 ~ 0.4 mm, and when the thickness of the mesh sheet is less than 0.2 mm, the three-dimensional fluid flow is disturbed and the decrease in the amount of filtered water can be reduced And, if it exceeds 0.6 mm, the membrane performance may be rather deteriorated.

And, the diameter of the first yarn and the second yarn included in the mesh sheet may be 0.1 ~ 0.3 mm, more preferably 0.125 ~ 0.2 mm, when the diameter of the first yarn and the second yarn is less than 0.1 mm , the three-dimensional fluid flow is disturbed, the reduction in the amount of filtered water may be reduced, and if it exceeds 0.3 mm, there may be a problem in that the thickness of the mesh sheet itself becomes too thick.

The first yarn and the second yarn included in the mesh sheet may be arranged so as to be parallel with an interval of 0.2 to 1.0 mm, more preferably 0.2 to 0.5 mm, if the spacing between the first yarn and the second yarn If it is less than 0.2 mm, the three-dimensional fluid flow may be disturbed and the decrease in the amount of filtered water may be reduced.

The first yarn and the second yarn may cross each other at an angle (θ) of 20 to 70°, more preferably 20 to 50°, and if the angle (θ) is less than 20°, it may be difficult to manufacture a module. There may be problems such as a decrease in the salt removal rate due to the occurrence of defects, and when it exceeds 70°, the three-dimensional fluid flow is disturbed by the first and second yarns, and the filtered water amount may be reduced. .

When manufacturing a spiral wound filter module, an epoxy-based adhesive is used as the adhesive used to form the joint. In general, an epoxy-based adhesive is superior to a polyurethane-based adhesive in terms of dissolution.

The spiral wound ultrafiltration module of the present invention described in detail above has a high packing density because the inner voids of the spiral wound filter packed in the housing are very low or few are packed. When the packing density of the spiral wound filter module of the present invention is measured based on Equation 1 below, the packing density may satisfy 80 to 99%, preferably 90 to 99%.

[Equation 1]

packing density = (A - B)/A × 100

In Equation 1, A is the inner volume of the unit cell (Inner Volume of Unit Cell), B is the volume of the packed water (Volume of Packing Water). In other words, the packing density can be calculated from the above formula by calculating the inner volume of the housing and measuring the amount of water filled therein.

Since the spiral wound type ultrafiltration module of the present invention has such a high packing density, unlike the ultrafiltration module using a hollow fiber membrane (packing density is about 60 to 90%), the high resistance to changes in external pressure, fluid flow, temperature, etc. It can have durability, and can secure excellent long-term durability against high-pressure operation and secure excellent filtering performance.

On the other hand, the use of less adhesive compared to the hollow fiber membrane module can solve the TOC generation problem during cleaning that occurs in the hollow fiber type ultrafiltration module.

The spiral wound ultrafiltration module of the present invention is washed with ultrapure water having a specific resistance of 18 MΩ or more and TOC 1 ppb or less, but the TOC concentration of the filtered water may be 1 ppb or less within 18 hours of module cleaning

The spiral wound ultrafiltration module of the present invention is very suitable for application as a final UF in the ultrapure water manufacturing process.

Hereinafter, the present invention will be described in more detail through examples. However, the following examples are provided to aid understanding of the present invention, and should not be construed as limiting the scope of the present invention by the following examples.

[Example]

Preparation Example 1: Preparation of polysulfone-based flat membrane

(1) Synthesis of sulfonated polysulfone-based polymer

50 g of a polysulfone-based polymer (Udel, P3500) was added to 520 ml of 1,2-dichloroethane and dissolved at 25° C., 9 ml of chlorosulfonic acid was diluted with 104 ml of 1,2-dichloroethane and slowly added, Stirred for 4 hours. To terminate the reaction, the remaining solvent is discarded, the polymer is washed with methanol, neutralized using water and 1N aqueous sodium hydroxide solution, and dried in a vacuum oven at 50° C. for more than 12 hours to achieve a sulfonation degree of 60%. A phone-based polymer was prepared (sulfonation degree 60%).

(2) flat membrane manufacturing

5% by weight of the sulfonated polysulfone-based polymer and 15% by weight of the polysulfone-based polymer were dissolved in 65% by weight of dimethylacetamide, and then 15% by weight of polyvinylpyrrolidone was added thereto in a bath at 50° C. for 12 hours. A polymer solution was prepared by stirring above.

The polymer solution was uniformly coated at a speed of 0.2 m/min so as to have a thickness of 100 to 120 μm on a stainless steel support at 8° C. After that, the mixture is exposed to air using a temperature range of 20 to 65 ° C and a humidity range of 30 to 80% using a gradient device to control the pores of the upper layer by treating the coated polymer solution, and the composition ratio of isopropyl alcohol/water is maintained constant. It was solidified by passing it through a solution coagulation bath. Thereafter, the membrane was peeled off the support, the remaining solvent components contained in the membrane were extracted in a water washing tank, and dried with air at 80° C. to prepare a polysulfone-based flat membrane.

Preparation Example 2: Preparation of tricot filter fabric

(1) Preparation of resin for the deep part

A first mixture was prepared by mixing terephthalic acid and 1,2-ethanediol in a molar ratio of 1:1.5 by esterification at 250°C. Thereafter, 0.03 parts by weight of antimony trioxide was added to the first mixture based on 100 parts by weight of the first mixture to prepare a resin for the deep part (PET resin) by polycondensation at 285°C.

(2) Manufacture of resin for the first layer

An acid component and an alcohol component were mixed in a molar ratio of 1:1.5 to prepare a second mixture by esterification at 250°C. Thereafter, 0.03 parts by weight of antimony trioxide was added to the second mixture based on 100 parts by weight of the second mixture to prepare a resin (polyester resin) for the first layer by polycondensation at 285°C.

(3) Manufacture of core-sheath type composite fiber

In order to prepare the core-sheath composite fiber, the resin for the deep part and the resin for the super-layer part were put into a composite spinneret in a weight ratio of 1:1 and melt-spun to prepare a core-sheath composite fiber.

(4) Preparation of tricot filter fabric

Dough was prepared with the core-sheath type composite fiber and pre-treated at 100° C. for 30 minutes with a batch-type preprocessor to remove impurities to prepare a tricot filter fabric. , DL-2015) and heat treatment was performed at a temperature of 180° C. for 15 minutes to prepare a heat-treated tricot filter fabric.

(5) Preparation of antimony eluted tricot filter fabric

In order to elute antimony, 1 L of distilled water and 3.2 mg of 0.5N nitric acid (HNO ₃ ) as an additive are put in a round flask of 1 L capacity, and 5 g of the tricot filter fabric is put in, and then sodium hydroxide (NaOH) is added so that the pH is 8. Titrated. After maintaining at 25 ° C. for 40 minutes, the circular knitted fabric was taken out. Thereafter, by passing high-pressure water through a complete inspection to remove residual nitric acid on the surface, a tricot filter fabric eluted with antimony was prepared (antimony removal rate of 94%).

Preparation example 3: mesh sheet

As an inner spacer, a polypropylene mesh sheet of the same size as the polysulfone-based flat membrane of Preparation Example 1 (thickness: 0.12 mm, spacing between first and second yarns: 0.3 mm, cross angle between first and second yarns: 60°) was prepared.

Example 1: Preparation of spiral wound type ultrafiltration module for manufacturing ultrapure water

(1) Manufacture of spiral wound filter module

Cut the polysulfone-based flat membrane, which is the membrane sheet 21, prepared in Preparation Example 1 on the tricot filter fabric prepared in Preparation Example 2, fold in half so that the polysulfone-based flat membranes come into contact with each other to prepare a separation membrane, and then between the folded separation membranes. The mesh sheet prepared in Preparation Example 3 of the same size as the separator was inserted into the

Next, the tricot of Preparation Example 2 was placed again on the upper part of the separation membrane, and an adhesive was applied to the edges except for the perforated tube 10 part.

The above process was repeated to prepare a sheet laminate 20 in which a separator and a spacer were laminated.

Next, the sheet laminate 20 is wound in a spiral wound shape by winding under pressure conditions, and then end caps are attached to both ends of the perforated tube 10, and the outside, where the separator is exposed, is made of epoxy and glass fiber. It was wound to manufacture a spiral wound type ultrafiltration module.

Then, the spiral wound type filter module was filled in the housing to manufacture a spiral wound type ultrafiltration module for producing ultrapure water.

Comparative Example 1: Hollow fiber membrane type ultrafiltration module

A hollow fiber membrane type ultrafiltration module (trade name: KU-1010HS) from Kurita was prepared.

Comparative Example 2: bare winding type ultrafiltration module

A spiral wound type ultrafiltration module in which a housing was filled with a spiral wound filter module prepared using the same tricot filter fabric and mesh sheet as in Example 1 was prepared by using a polyethylene sulfone flat membrane instead of the polysulfone-based flat membrane of Preparation Example 1 ( Toray's trade name UE4040-ES10).

Experimental Example 1

Time taken to complete module cleaning by filtration of ultra-pure water in the ultrafiltration module of Example 1 and Comparative Examples 1 and 2 under the conditions shown in Table 1 below to measure TOC elution time, specific resistance, and the number of particles in the produced water, respectively were compared. The results are shown in Tables 1 and 2 below.

At this time, the TOC measuring instrument is a Sievers Check Point of GE, and it is possible to measure from 0.05 to 1,000 μg/L.

And, the specific resistance was measured using M300 manufactured by Mettler Toledo, and the measurement range was 0.02 to 50,000 μs/cm.

In addition, the number of particles in influent and produced water was measured using Rion's XP-L4A1 model, and the detection range was 0 ~ 1,000 ea/mL. The removal rate was determined.

In addition, the results of measuring the number of particles in the produced water according to the flux of the Hanwa filtration module of Example 1 and Comparative Example 1 are shown in FIG. 8 .

division Comparative Example 1 Comparative Example 2 Example 1 number of membranes One 2 2 permeate flow rate 108 m ³ /day 5.5 m ³ /day 13.2 m ³ /day effective membrane area 5 m ² 15.8 m ² (7.9 m ² /1 unit) 15.8 m ²
(7.9 m ² /1 unit) facility flow 2.06 m ³ /hr 0.74 m ³ /hr 1.52 m ³ /hr inlet pressure 0.27 Mpa 0.44 Mpa 0.36 Mpa Flux (LMH) 412 47 96 Non-flux (LMH bar) 154 11 27 TOC dissolution time 42 hours 19.2 hours 18.0 hr number of particles produced 0.55 EA/ml 262 EA/ml 0.90 EA/ml

In addition, by changing the number of pumps and/or PCV set values of the ultrafiltration module of Example 1 and Comparative Example 1, the number of particles of flux, non-flux and produced water was measured in the same manner as in Experimental Example 1, and the results were It is shown in Table 2 and Table 3 below. At this time, the concentrated water flow rate was 0.1 m ² /hr.

And, the results of measuring the flux according to the differential pressure of the incoming and produced water in Example 1 and Comparative Examples 1 and 2 are shown in FIG. 9 .

division Example 1
(1 pump) Example 1
(2 pumps) number of modules 2 2 membrane area ^(One) 15.8 m ²
(7.9 m ² /1 unit) 15.8 m ²
(7.9 m ² /1 unit) PCV ⁽²⁾ Set value (MPa) 0.2 0.1 0.05 0.2 0.1 0.05 Production water flow (L/hr) 1520 1710 1880 1680 2030 2110 Inlet pressure (bar) 3.55 3.2 2.89 3.6 3.12 3 Concentrate pressure (bar) 3.45 3 2.7 3.45 2.90 2.78 Production water pressure (bar) 2 One 0.5 2 One 0.5 Inlet and production water pressure (bar) 1.55 2.25 2.39 1.6 2.12 2.5 Flux (L/m ² hr=LMH) 96 108 119 106 128 134 Non-flux (LMH bar) 27 34 41 30 41 45 Produced water particle count (EA/ml) 0.90 0.95 0.70 0.77 0.53 0.70 (1) Membrane area: It means the effective membrane area that can actually be filtered when the flat membrane is modularized.
(2)PCV (Pressure Control Valve): The value of the valve that controls the pressure of the filtered water (supply pressure control valve). As the valve value decreases, the supply pressure decreases and the production quantity increases.

division Comparative Example 1
(1 pump) Comparative Example 1
(2 pumps) number of membranes One One membrane area ^(One) 5 m ² 5 m ² PCV ⁽²⁾ Set value (MPa) 0.2 0.1 0.05 0.2 0.1 0.05 Production water flow (L/hr) 2060 2420 2640 2270 2660 2860 Inlet pressure (bar) 2.68 1.97 1.55 2.78 2.07 1.72 Concentrate pressure (bar) 26.3 1.88 1.45 2.7 1.95 1.58 Production water pressure (bar) 2 0.1 0.5 0.2 0.1 0.05 Inlet and production water pressure (bar) 0.68 1.87 1.05 2.58 1.97 1.67 Flux (L/m ² hr=LMH) 412 484 528 454 532 572 Non-flux (LMH bar) 154 246 341 163 257 333 Produced water particle count (EA/ml) 0.55 0.98 0.55 0.89 0.93 1.22 (1) Membrane area: It means the effective membrane area that can actually be filtered when the flat membrane is modularized.
(2) PCV (Pressure Control Valve): A valve value that controls the pressure of the filtered water (supply pressure control valve). As the valve value decreases, the supply pressure decreases and the production quantity increases.

10: perforated pipe 12: inlet hole
21: membrane sheet 22: permeate passage sheet
20: sheet laminate 30: joint

Claims (10)

housing; and a spiral wound filter module packed in the housing;
When the packing density of the spiral wound filter module is measured based on Equation 1 below, the spiral wound type ultrafiltration module for manufacturing ultrapure water, characterized in that 80 to 99%.
[Equation 1]
packing density = (A - B)/A × 100
In Equation 1, A is the inner volume of the unit cell (Inner Volume of Unit Cell), B is the volume of the packed water (Volume of Packing Water).
The spiral wound type ultrafiltration module for producing ultrapure water according to claim 1, wherein the total organic carbon (TOC) of the washed filtered water is 1 ppb or less within 18 hours after washing with ultrapure water having a specific resistance of 18 MΩ or more.
According to claim 1, wherein the spiral wound filter module
a perforated tube having at least one inlet hole;
a cylindrical filter body in which a membrane sheet and a permeate passage sheet are sequentially stacked in multiple layers and wound in a spiral wound on the outer surface of the perforated tube; and
Including; a joint for bonding the membrane sheet and the sheet through the permeate passage;
The joint portion is a joint connection connecting a pair of joint extension lines extending in parallel along both sides of the edge of at least one of the membrane sheet and the permeate passage sheet and the end ends of the pair of joint extension lines facing each other A spiral wound type ultrafiltration module for manufacturing ultra-pure water, characterized in that it includes a line and a bent line bent in a direction opposite to each other so as to be close to the inlet hole from the start end of a pair of joint extension lines corresponding to the line and the perforated tube.
[4] The spiral wound type ultrafiltration module for manufacturing ultrapure water according to claim 3, further comprising a fusion part for temporarily fixing the sheet laminate at a position corresponding to a position between the outer edge of the cylindrical filter body and the joining extension line.
[Claim 4] The spiral wound type ultrafiltration module for manufacturing ultrapure water according to claim 3, wherein the outer surfaces of both ends of the perforated tube include at least one groove in which a portion of the adhesive flowing out from the joint interposed between the sheet laminates is accommodated.
[Claim 6] The spiral wound type ultrafiltration module for producing ultrapure water according to claim 5, wherein the groove includes an absorbent member that absorbs a portion of the adhesive.
4. The method of claim 3, wherein the membrane sheet independently comprises a polysulfone flat membrane;
The permeate passage sheet includes a tricot filter fabric,
The spiral wound type ultrafiltration module for manufacturing ultrapure water, characterized in that the multi-layered sheet laminate is adjacent to each other and a mesh sheet is placed between the membrane sheets of the laminated sheet laminate.
The spiral wound type ultrafiltration module for producing ultrapure water according to claim 3, wherein the joint part comprises an epoxy-based adhesive resin.
The method of claim 7, wherein the polysulfone flat membrane
It is prepared from a polymer solution containing a sulfonated polysulfone-based polymer, a polysulfone-based polymer and a solvent,
The polysulfone-based polymer comprises at least one selected from a polysulfone polymer, a polyethersulfone polymer and a polyallyl ethersulfone polymer.
An ultrapure water production system using the spiral wound type ultrafiltration module of any one of claims 1 to 9.

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