KR102054544B1 - Method for manufacturing water-treatment membrane, water-treatment membrane manufactured by thereof, and water treatment module comprising membrane - Google Patents

Abstract

The present specification provides a water treatment module including a method of manufacturing a water treatment separator, a water treatment separator manufactured using the same, and a water treatment separator.

Description

Method for manufacturing a water treatment membrane and a water treatment module comprising the water treatment membrane and the water treatment membrane produced by the present invention TECHNICAL FOR MANUFACTURING WATER-TREATMENT MEMBRANE, WATER-TREATMENT MEMBRANE MANUFACTURED BY THEREOF, AND Water Termination Module

The present specification provides a water treatment module including a method of manufacturing a water treatment separator, a water treatment separator manufactured using the same, and a water treatment separator.

Due to the recent severe pollution and lack of water in the water environment, the development of new water resources is an urgent challenge. Water pollution research aims to treat high quality living and industrial water, various kinds of domestic sewage and industrial wastewater, and interest in water treatment processes using membranes with advantages of energy saving is increasing. In addition, accelerating environmental regulations are expected to accelerate membrane technology. Conventional water treatment processes are difficult to meet the tightening regulations, but the membrane technology is expected to become a leading technology in the future because of the excellent treatment efficiency and stable treatment.

Liquid separation is classified into Micro Filtration, Ultra Filtration, Nano Filtration, Reverse Osmosis, Sedimentation, Active Transport and Electrodialysis depending on the pore of the membrane. The reverse osmosis method refers to a process of desalting using a semipermeable membrane that transmits water but is impermeable to salt. When the high pressure water in which the salt is dissolved flows into one side of the semipermeable membrane, the pure water is removed. Will come out on the other side at low pressure.

In recent years, about 1 billion gal / day of water worldwide has undergone desalination through reverse osmosis, and since the first desalination using reverse osmosis was introduced in the 1930s, many of the The study was conducted. Among them, the main successes of commercial success are cellulose-based asymmetric membranes and polyamide-based composite membranes. Cellulose membranes developed in the early stages of reverse osmosis membranes have suffered from several shortcomings due to their narrow operating pH range, their deformation at high temperatures, the high cost of operation using high pressure, and their vulnerability to microorganisms. This is a rarely used trend.

On the other hand, in the polyamide composite membrane, a polysulfone layer is formed on a nonwoven fabric to form a microporous support, and the microporous support is immersed in an aqueous solution of m-phenylenediamine (mPD) to form an mPD layer. After forming, it is immersed or coated in a trimesoyl chloride (TMC) organic solution, and the mPD layer is contacted with TMC to prepare a polyamide active layer. By contacting the nonpolar and polar solutions, the polymerization takes place only at the interface to form a very thin polyamide layer. The polyamide-based composite membrane has a high stability against pH changes, can be operated at low pressure, and has a high salt removal rate, compared to existing cellulose-based asymmetric membranes.

Research on improving the performance of such a polyamide composite membrane has been continuously made.

Korean public publication 10-1999-0019008

The present specification is to provide an improved performance water treatment membrane and its preparation method.

One embodiment of the present specification, preparing a porous support; And forming a polyamide active layer on the porous support by using interfacial polymerization of an aqueous solution containing an amine compound and an organic solution containing an acyl halide compound.

The aqueous solution provides a method of preparing a water treatment membrane further comprising a compound represented by the following formula (1).

[Formula 1]

In Chemical Formula 1,

R1 to R4 are the same as or different from each other, and each independently hydrogen, deuterium, a halogen group, or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.

An exemplary embodiment of the present specification provides a water treatment separation membrane manufactured according to the manufacturing method.

One embodiment of the present specification, a porous support; And a polyamide active layer provided on the porous support,

The polyamide active layer provides a water treatment separation membrane including the compound represented by Chemical Formula 1.

An exemplary embodiment of the present specification provides a water treatment module including at least one of the water treatment separation membranes.

The water treatment membrane prepared by the manufacturing method according to one embodiment of the present specification shows excellent salt removal rate.

Furthermore, the water treatment separator prepared by the manufacturing method according to one embodiment of the present specification shows high boron removal rate with high salt removal rate.

In addition, the manufacturing method according to one embodiment of the present specification has an advantage of significantly lowering the amount of pollutants generated during the manufacturing process.

1 illustrates a water treatment separation membrane according to an exemplary embodiment of the present specification.

In this specification, when a member is located "on" another member, this includes not only when a member is in contact with another member but also when another member exists between the two members.

In the present specification, when a part "includes" a certain component, this means that the component may further include other components, except for the case where there is no description to the contrary.

The present inventors have developed a water treatment separation membrane having excellent boron removal rate and salt removal rate using the compound represented by the following Chemical Formula 1. The compound represented by the following Chemical Formula 1 does not have a charge and does not have a polymer form, so that the compound is well dispersed in an aqueous solution during preparation. Furthermore, the compound represented by Formula 1 may minimize the generation of precipitates in the aqueous solution, it is possible to minimize the contaminants generated in the manufacturing process. In addition, the following water treatment separation membranes developed by the present inventors exhibit an improved boron removal rate of 0.1% or more compared with the case in which the compound represented by Chemical Formula 1 is not applied, and thus can exhibit high boron removal performance as compared to the conventional water treatment separation membrane.

Hereinafter, this specification is demonstrated in detail.

One embodiment of the present specification, preparing a porous support; And forming a polyamide active layer on the porous support by using interfacial polymerization of an aqueous solution containing an amine compound and an organic solution containing an acyl halide compound.

The aqueous solution provides a method of preparing a water treatment membrane further comprising a compound represented by the following formula (1).

[Formula 1]

In Chemical Formula 1,

R1 to R4 are the same as or different from each other, and each independently hydrogen, deuterium, a halogen group, or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.

According to an exemplary embodiment of the present specification, R1 and R2 may each be hydrogen.

According to an exemplary embodiment of the present specification, R3 and R4 may be a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, respectively.

According to an exemplary embodiment of the present specification, the alkyl group may be linear, branched or cyclic. In addition, according to an exemplary embodiment of the present specification, the alkyl group is a methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group, iso- Pentyl group, neo-pentyl group, n-hexyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group or cyclohexyl group. However, the present invention is not limited thereto.

According to an exemplary embodiment of the present specification, the halogen group may be fluorine, chlorine, bromine or iodine.

The "substituted or unsubstituted" is halogen, nitrile, nitro, hydroxy, alkyl, cycloalkyl, alkenyl, alkoxy, aryloxy, thiol, alkylthio, allylthio, sulfoxy, alkyl sulfoxide Group consisting of an aryl sulfoxy group, a silyl group, a boron group, an arylamine group, an aralkylamine group, an alkylamine group, an aryl group, a fluorenyl group, a carbazole group, an arylalkyl group, an arylalkenyl group, a heterocyclic group, and an acetylene group It means that it is substituted with one or more substituents selected from, or has no substituent.

According to an exemplary embodiment of the present specification, the content of the compound represented by Formula 1 may be 0.01 wt% or more and 5 wt% or less with respect to the aqueous solution.

According to one embodiment of the present specification, the aqueous solution may further include a surfactant.

According to one embodiment of the present specification, the surfactant may be selected from nonionic, cationic, anionic and amphoteric surfactants. According to an exemplary embodiment of the present specification, the surfactant is sodium lauryl sulfate (SLS), alkyl ether sulfates, alkyl sulfates, olefin sulfonates, alkyl ether carboxylates, sulfosuccinates, aromatic sulfo Alkyl polyglucosi such as nates, octylphenol ethoxylates, ethoxylated nonylphenols, copolymers of alkyl poly (ethylene oxide), poly (ethylene oxide) and poly (propylene oxide), octyl glucoside or decyl maltoside Fatty acid alcohols such as Drew, cetyl alcohol or oleyl alcohol, cocamide MEA, cocamide DEA, alkyl hydroxyethyl dimethyl ammonium chloride, cetyltrimethyl ammonium bromide or chloride, hexadecyltrimethylammonium bromide or chloride, and alkyl betaines Include. Specifically, according to one embodiment of the present specification, the surfactant may be SLS, octylphenol ethoxylates or ethoxylated nonylphenols.

According to an exemplary embodiment of the present specification, the content of the surfactant may be 0.005 wt% or more and 0.5 wt% or less with respect to the aqueous solution.

An exemplary embodiment of the present specification provides a water treatment membrane manufactured by the manufacturing method.

One embodiment of the present specification, a porous support; And a polyamide active layer provided on the porous support,

The polyamide active layer provides a water treatment separation membrane including the compound represented by Chemical Formula 1.

According to an exemplary embodiment of the present specification, the boron removal rate of the water treatment separation membrane may be improved by at least 0.1% compared to the boron removal rate when the compound represented by Formula 1 is not included in the polyamide active layer.

According to an exemplary embodiment of the present specification, the boron removal rate (Boron Rejection) of the water treatment separation membrane may be 90% or more.

According to an exemplary embodiment of the present specification, the salt rejection (Salt Rejection) of the water treatment membrane may be 99.5% or more, 99.8% or more, or 99.9% or more.

1 illustrates a water treatment separation membrane according to an exemplary embodiment of the present specification. Specifically, FIG. 1 illustrates a water treatment separator in which the nonwoven fabric 100, the porous support 200, and the polyamide active layer 300 are sequentially provided, and the brine 400 is introduced into the polyamide active layer 300. Purified water 500 is discharged through the nonwoven fabric 100, the concentrated water 600 is not passed through the polyamide active layer 300 is discharged to the outside. However, the water treatment membrane according to one embodiment of the present specification is not limited to the structure of FIG. 1, and may further include an additional configuration.

According to one embodiment of the present specification, as the porous support, a coating layer of a polymer material may be used on a nonwoven fabric. Examples of the polymer material include polysulfone, polyethersulfone, polycarbonate, polyethylene oxide, polyimide, polyetherimide, polyether ether ketone, polypropylene, polymethylpentene, polymethyl chloride and polyvinylidene fluorine. Ride or the like may be used, but is not necessarily limited thereto. Specifically, polysulfone may be used as the polymer material.

According to one embodiment of the present specification, the polyamide active layer may be formed through interfacial polymerization of an aqueous solution containing an amine compound and an organic solution containing an acyl halide compound. Specifically, the polyamide active layer comprises the steps of forming an aqueous layer including an amine compound on the porous support; And an organic solution including an acyl halide compound and an organic solvent on the aqueous solution layer including the amine compound, to form a polyamide active layer.

Upon contact between the aqueous solution layer containing the amine compound and the organic solution, the amine compound and acyl halide compound coated on the surface of the porous support react with each other to generate polyamide by interfacial polymerization, and are adsorbed onto the microporous support to form a thin film. Is formed. In the contact method, the polyamide active layer may be formed through a method such as dipping, spraying or coating.

According to one embodiment of the present specification, a method of forming an aqueous solution layer including an amine compound on the porous support is not particularly limited, and any method capable of forming an aqueous solution layer on the support may be used without limitation. Specifically, the method of forming the aqueous solution layer containing an amine compound on the porous support may be sprayed, applied, immersed, dripping and the like.

In this case, the aqueous solution layer may be further subjected to the step of removing the aqueous solution containing the excess amine compound as necessary. The aqueous solution layer formed on the porous support may be unevenly distributed when there are too many aqueous solutions present on the support. When the aqueous solution is unevenly distributed, a nonuniform polyamide active layer may be formed by subsequent interfacial polymerization. have. Therefore, it is preferable to remove excess aqueous solution after forming an aqueous solution layer on the said support body. The removal of the excess aqueous solution is not particularly limited, but may be performed using, for example, a sponge, air knife, nitrogen gas blowing, natural drying, or a compression roll.

According to an exemplary embodiment of the present specification, the amine compound in the aqueous solution containing the amine compound is not limited if the amine compound used in the water treatment separation membrane manufacturing, to give a specific example, m-phenylenediamine, p -Phenylenediamine, 1,3,6-benzenetriamine, 4-chloro-1,3-phenylenediamine, 6-chloro-1,3-phenylenediamine, 3-chloro-1,4-phenylene diamine Or a mixture thereof.

According to an exemplary embodiment of the present specification, the acyl halide compound is not limited thereto, but may be, for example, an aromatic compound having 2 to 3 carboxylic acid halides, such as trimezoyl chloride, isophthaloyl chloride and At least one mixture selected from the group of compounds consisting of terephthaloyl chloride.

According to an exemplary embodiment of the present specification, the organic solvent is an aliphatic hydrocarbon solvent, for example, a hydrophobic liquid which is not mixed with freons and water such as hexane, cyclohexane, heptane, and alkanes having 5 to 12 carbon atoms, for example. For example, alkanes having 5 to 12 carbon atoms and mixtures thereof, such as IsoPar (Exxon), IsoPar G (Exxon), ISOL-C (SK Chem), ISOL-G (Exxon), and the like may be used, but are not limited thereto.

According to one embodiment of the present specification, the water treatment separation membrane may be used as a micro filtration membrane, an ultra filtration membrane, an ultra filtration membrane, a nano filtration membrane, a reverse osmosis membrane, or a reverse osmosis membrane. Can be used.

In addition, an exemplary embodiment of the present specification provides a water treatment module including at least one of the water treatment separation membrane.

A specific kind of the water treatment module is not particularly limited, and examples thereof include a plate & frame module, a tubular module, a hollow & fiber module or a spiral wound module. In addition, as long as the water treatment module includes the water treatment separation membrane according to one embodiment of the present specification described above, other configurations and manufacturing methods are not particularly limited, and general means known in the art may be employed without limitation. have.

Meanwhile, the water treatment module according to one embodiment of the present specification has excellent salt removal rate and permeation flow rate, and has excellent chemical stability, and thus may be usefully used for water treatment devices such as household / industrial water purification devices, sewage treatment devices, seawater treatment devices, and the like. have.

Hereinafter, the present invention will be described in detail with reference to Examples. However, embodiments according to the present disclosure may be modified in various other forms, and the scope of the present disclosure is not interpreted to be limited to the embodiments described below. The embodiments of the present specification are provided to more fully describe the present specification to those skilled in the art.

[ Example  One]

18% by weight of polysulfone solids were added to a DMF (N, N-dimethylformamide) solution and dissolved at 80 ° C. to 85 ° C. for at least 12 hours to obtain a uniform liquid phase. This solution was cast 150 μm thick on a 95 μm to 100 μm thick nonwoven fabric made of polyester. Then, the cast nonwoven fabric was put in water to prepare a porous polysulfone support.

An aqueous solution containing metaphenylenediamine (mPD) and 0.1 wt% of DMH (5,5-dimethyl-2,4-imidazolidinedione) was applied onto the porous polysulfone support by a slot coating method to form an aqueous solution layer. Furthermore, the excess aqueous solution generated at the time of application was removed using an air knife, and then an organic solution containing IsoPar G (Exxon), mesitylene, and trimesoyl chloride (TMC) was applied onto the aqueous layer. Then, after drying until all the liquid components evaporated at 95 ℃, washed with ultra pure distilled water (DIW) to prepare a water treatment membrane.

 [ Example  2]

DMH (5,5-dimethyl-2,4-imidazolidinedione) content of the aqueous solution was prepared in the same manner as in Example 1 except that it was adjusted to 0.4 wt%.

[ Comparative example  One]

A water treatment separation membrane was manufactured in the same manner as in Example 1, except that 0.1 wt% of PHB ((poly) hexamethylene biguanide) instead of DMH was included in the aqueous solution.

[ Experimental Example ]

The brine containing 32,000 ppm NaCl and 5 ppm boron was used to evaluate the performance of the water treatment membranes prepared according to the Examples and Comparative Examples under 800 psi. The salt removal rate was measured by measuring the conductivity difference between the produced water and the raw water, and the permeate flux (Flux) was calculated by measuring the volume of produced water secured per unit time (5 minutes). In addition, the boron removal rate was calculated by measuring the difference between the boron content using ICP-OES in the production and raw water.

The performance of the water treatment membrane according to the measured examples and comparative examples are as shown in Table 1 below.

Salt removal rate
(%) Permeate flow rate
(GFD) Boron removal rate
(%) Example 1 99.9 19 90 Example 2 99.9 21 92 Comparative Example 1 99.8 18 89

The GFD of the permeate flow rate means gallon / ft ² · day.

According to Table 1, the water treatment separation membrane according to the embodiment can be seen that the salt removal rate and boron removal rate is superior to the comparative example. Furthermore, it can be seen that the permeate flow rate of the water treatment separation membrane according to the embodiment is also superior to that of the comparative example.

100: non-woven
200: porous support
300: polyamide active layer
400: brine
500: purified water
600: concentrated water

Claims (7)

Preparing a porous support; And
Forming an polyamide active layer on the porous support by using interfacial polymerization of an aqueous solution containing an amine compound and an organic solution containing an acyl halide compound,
The amine compound is m-phenylenediamine (m-PD),
The aqueous solution is a method for producing a water treatment separation membrane further comprising a compound represented by the formula (1):
[Formula 1]

In Chemical Formula 1,
R1 to R4 are the same as or different from each other, and each independently hydrogen, deuterium, a halogen group, or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms. The method according to claim 1,
The content of the compound represented by the formula (1) is 0.01 wt% or more 5 wt% or less with respect to the aqueous solution. The method according to claim 1,
The aqueous solution is a method of producing a water treatment separation membrane further comprising a surfactant. The method according to claim 3,
The amount of the surfactant is 0.005 wt% or more to 0.5 wt% or less with respect to the aqueous solution. delete delete delete

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