KR101991433B1 - Method for manufacturing water-treatment membrane, water-treatment membrane manufactured by thereof, and water treatment module comprising membrane - Google Patents
Method for manufacturing water-treatment membrane, water-treatment membrane manufactured by thereof, and water treatment module comprising membrane Download PDFInfo
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- KR101991433B1 KR101991433B1 KR1020150114878A KR20150114878A KR101991433B1 KR 101991433 B1 KR101991433 B1 KR 101991433B1 KR 1020150114878 A KR1020150114878 A KR 1020150114878A KR 20150114878 A KR20150114878 A KR 20150114878A KR 101991433 B1 KR101991433 B1 KR 101991433B1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/56—Polyamides, e.g. polyester-amides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/025—Reverse osmosis; Hyperfiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
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- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The present invention relates to a method for manufacturing a water treatment membrane, a water treatment membrane manufactured using the same, and a water treatment module including a membrane.
Description
The present invention provides a water treatment module including a method for manufacturing a water treatment membrane, a water treatment membrane manufactured using the same, and a water treatment membrane.
Due to the serious pollution and water shortage in recent years, it is urgent to develop new water resources. Studies on the pollution of water quality are aiming at the treatment of high quality living and industrial water, various domestic sewage and industrial wastewater, and interest in the water treatment process using the separation membrane having the advantage of energy saving is increasing. In addition, the accelerated enforcement of environmental regulations is expected to accelerate the activation of membrane technology. Conventional water treatment process is difficult to meet the regulations that are strengthened, but membrane technology is expected to become a leading technology in the water treatment field because it guarantees excellent treatment efficiency and stable treatment.
Liquid separation is classified into micro filtration, ultrafiltration, nano filtration, reverse osmosis, sedimentation, active transport and electrodialysis depending on the pores of the membrane. Among them, the reverse osmosis method refers to a process of desalting using a semi-permeable membrane which is permeable to water but impermeable to salt. When high-pressure water containing salt is introduced into one side of the semipermeable membrane, Will come out on the other side with low pressure.
In recent years, approximately 1 billion gal / day of water has been subjected to dechlorination through the reverse osmosis process. Since the first reverse osmosis process using the reverse osmosis in the 1930s was announced, many of the semi- Research was conducted. Among them, cellulose-based asymmetric membranes and polyamide-based composite membranes are the main commercial successes. The cellulosic membranes developed at the beginning of the reverse osmosis membrane have various drawbacks such as narrow operating pH range, high temperature deformation, high cost of operation due to high pressure, and vulnerability to microorganisms Is a rarely used trend.
On the other hand, the polyamide-based composite membrane is formed by forming a polysulfone layer on a nonwoven fabric to form a microporous support, and immersing the microporous support in an aqueous solution of m-phenylenediamine (hereinafter referred to as mPD) And then the resultant is immersed or coated in an organic solution of triMesoyl Chloride (hereinafter referred to as TMC) to form a polyamide active layer by interfacial polymerization with the mPD layer in contact with TMC. By contacting the nonpolar solution with the polar solution, the polymerization takes place at the interface only and forms a very thin polyamide layer. The polyamide-based composite membrane has higher stability against pH change, can operate at lower pressure, and has a higher salt removal rate than conventional cellulose-based asymmetric membranes, and is currently a mainstream of water treatment membranes.
Studies on increasing the salt removal rate and permeate flow rate of such polyamide composite membranes have been continuously carried out.
The present invention provides a method for manufacturing a water treatment membrane capable of improving performance through a simple process and a water treatment membrane manufactured using the same.
One embodiment of the present disclosure relates to a method of preparing a porous support, comprising: preparing a porous support; Preparing an aqueous solution containing an amine compound; Preparing an organic solution comprising an acyl halide compound, a non-polar aprotic solvent, a polar aprotic solvent, and a polar quantum solvent; Forming an aqueous solution layer on the porous support using the aqueous solution; And contacting the organic solution on the aqueous solution layer to form a polyamide active layer.
In addition, one embodiment of the present invention provides a water treatment separation membrane manufactured using the method for producing a water treatment separation membrane.
An embodiment of the present disclosure includes a porous support; And a polyamide active layer provided on the porous support, wherein the oxygen content of the polyamide active layer of the water treatment separation membrane is 20 wt% or more and 30 wt% or less.
In addition, one embodiment of the present disclosure provides a water treatment module comprising at least one water treatment separation membrane.
The method of manufacturing the water treatment separation membrane according to one embodiment of the present invention can improve the performance of the water treatment separation membrane by modifying the surface of the polyamide active layer by adding a simple process.
Specifically, the water treatment separator manufactured according to the method of manufacturing a water treatment separator according to one embodiment of the present invention has a high flux transmission rate while maintaining a high rejection of salt.
When a member is referred to herein as being "on " another member, it includes not only a member in contact with another member but also another member between the two members.
Whenever a component is referred to as "comprising ", it is to be understood that the component may include other components as well, without departing from the scope of the present invention.
Hereinafter, the present invention will be described in more detail.
One embodiment of the present disclosure relates to a method of preparing a porous support, comprising: preparing a porous support; Preparing an aqueous solution containing an amine compound; Preparing an organic solution comprising an acyl halide compound, a non-polar aprotic solvent, a polar aprotic solvent, and a polar quantum solvent; Forming an aqueous solution layer on the porous support using the aqueous solution; And contacting the organic solution on the aqueous solution layer to form a polyamide active layer.
The inventors of the present invention have completed studies for improving the water removal membrane salt removal rate and permeation flow rate including the polyamide-based active layer, and completed the process for producing the water treatment separation membrane. Specifically, the method for producing a water treatment separation membrane according to one embodiment of the present invention comprises oxidizing an acyl halide compound of an organic solution, forming a polyamide active layer by an interfacial polymerization with an aqueous solution containing an amine compound, It is possible to produce a water treatment separation membrane having a good permeation flux (Flux) while maintaining the rejection.
According to one embodiment of the present invention, the step of preparing the organic solution may include dissolving the acyl halide compound in the non-polar aprotic solvent, and then mixing the polar aprotic solvent and the polar protic solvent.
The non-polar aprotic solvent is for dissolving the acyl halide compound. Specifically, according to one embodiment of the present disclosure, the non-polar aprotic solvent includes an aliphatic hydrocarbon solvent, for example, a mixture of Freons and water such as hexane, cyclohexane, heptane, and alkane having 5 to 12 carbon atoms IsoPar (Exxon), ISOL-C (SK Chem), ISOL-G (Exxon) and the like, which are hydrophobic liquids, for example, alkanes having 5 to 12 carbon atoms and mixtures thereof may be used.
The polar aprotic solvent may inhibit the occurrence of the phase separation phenomenon between the polar aprotic solvent and the nonpolar aprotic solvent so that the polar aprotic solvent can oxidize the acyl halide compound. Specifically, in the case of mixing the non-polar aprotic solvent and the polar quantum solvent, except for the polar aprotic solvent, the polar protic solvent and the polar aprotic solvent are separated by the phase separation of the non-polar aprotic solvent and the polar aprotic solvent, The acyl halide compound may be difficult to react.
The polar protic solvent may oxidize the acyl halide compound to improve the hydrophilicity of the acyl halide compound. This makes it possible to increase the hydrophilicity of the polyamide active layer to be produced, thereby improving the permeation flow rate.
In addition, the polar protic solvent may partially oxidize the substituent of the acyl halide compound and prevent the oxidized substituent from bonding with the amine compound, thereby making the void of the chain structure formed through the interfacial polymerization larger. Specifically, the polar protic solvent can convert TMC to hydrolyzed TMC. That is, the polar protonic solvent can change one or two -COCl groups of TMC to -COOH, thereby preventing the reaction with the amine compound mPD. Accordingly, the voids of the chain structure of the polyamide active layer formed through the interfacial polymerization can be greatly controlled, and the effect of increasing the permeation flow rate can be obtained. Further, through such an oxidation process, the polyamide active layer of the water treatment separator according to the present invention can have a high oxygen content.
According to one embodiment of the present invention, the polar aprotic solvent may include at least one selected from the group consisting of a ketone solvent, an ester solvent, a cyan solvent, and a sulfoxide solvent.
Specifically, according to one embodiment of the present disclosure, the polar aprotic solvent is selected from the group consisting of acetone, methyl isobutyl ketone, butanone, 3-pentanone, 2 2-pentanone, ethyl isopropyl ketone, 3-methyl-2-pentanone, 2-hexanone, mesityl oxide (such as mesityl oxide, isophorone, acetophenone, cyclopentanone, tetrahydrofuran, ethyl acetate, allyl hexanoate, benzyl acetate benzyl acetate, butyl acetate, butyl butyrate, ethyl benzoate, ethyl butyrate, ethyl hexanoate, ethyl cinnamate, Ethyl formate, ethyl heptanoate, But are not limited to, ethyl isovalerate, ethyl lactate, ethyl nonanoate, ethyl pentanoate, isobutyl acetate, isobutyl formate ), Isopropyl acetate, methyl acetate, methyl benzoate, methyl butyrate, methyl cinnamate, methyl pentanoate, methyl But are not limited to, methyl phenyl acetate, octyl acetate, octyl butyrate, pentyl acetate, pentyl butyrate, pentyl hexanoate, pentyl pentanoate, propyl acetate, propyl hexanoate, propyl isobutyrate, dimethylformamide, (dimethyl formamide), N- (2,4, -dimethyl phenyl) formamide, N- (phenethyl) formamide, (2-hydroxyethyl) formamide, N- (1-phentyl) formamide, N- (4-methoxyphenyl) (4-methoxyphenyl) formamide, acetonitrile, benzonitrile, 3,4-dihydroxybenzonitrile, 2-amino-2-methyl 2-methyl propanenitrile, mandelonitrile, N- (cyanomethyl) acetamide, 3-pyridinecarbonitrile, 4 But are not limited to, 4-pyridinecarbonitrile, propionitrile, benzyl cyanide, succinonitrile, dimethyl sulfoxide, methyl phenyl sulfoxide, Diphenyl sulfoxide But are not limited to, diphenyl sulfoxide, p-tolyl sulfoxide, 4-chlorophenyl sulfoxide, methyl p-tolyl sulfoxide, butyl sulfoxide, and the like.
More specifically, according to one embodiment of the present disclosure, the polar aprotic solvent may be acetone, methyl isobutyl ketone, mesityl oxide, isophorone, tetrahydrofuran, dimethylformamide, dimethylsulfoxide.
According to one embodiment of the present invention, the polar protic solvent may include at least one selected from the group consisting of a carboxylic acid solvent, an alcohol solvent, water, and an amine solvent.
In particular, according to one embodiment of the present disclosure, the polar protic solvent is selected from the group consisting of methanoic acid, ethanoic acid, propanoic acid, butanoic acid, pentanoic acid, The present invention relates to a process for the preparation of a compound of formula (I) wherein R 1 is selected from the group consisting of hydrogen, acyl, acyl, acyl, acyl, acyl, acyl, acyl, acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid ), Acetoacetic acid, pyruvic acid, citric acid, glyceric acid, glycolic acid, lactic acid, chloroacetic acid, dichloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, oxalic acid, 2-hydroxyethanoic acid, propanedioic acid, 2- 2-methylpropanoic acid, butanedioic acid, butene- butanedioic acid, pentanedioic acid, hexanedioic acid, heptanedioic acid, methanol, ethanol, isopropyl alcohol, butyl alcohol, Pentanol, hexadecan-1-ol, ethane-1,2-diol, propane-1,2-diol, 2-diol, propane-1,2,3-triol, butane-1,2,3,4- tetraol, pentane-1,2,3,4,5-pentol, hexane-1,2,3,4,5,6- 1,2,3,4,5,6-hexol), heptane-1,2,3,4,5,6,7-heptol (heptane-1,2,3,4,5,6,7-heptol ), Water (H 2 O), and the like.
More specifically, according to one embodiment of the present disclosure, the polar protic solvent may be methanol, ethanol, water, butyl alcohol, trifluoroacetic acid, ethane.
According to one embodiment of the present invention, the content of the polar aprotic solvent may be 0.1 wt% or more and 5 wt% or less with respect to the organic solution. Specifically, according to one embodiment of the present invention, the content of the polar aprotic solvent may be 0.2 wt% or more and 4 wt% or less with respect to the organic solution. More specifically, according to one embodiment of the present disclosure, the content of the polar aprotic solvent may be 0.5 wt% or more and 3 wt% or less with respect to the organic solution.
When the content of the polar aprotic solvent is within the above range, occurrence of the phase separation phenomenon between the polar aprotic solvent and the nonpolar aprotic solvent can be effectively suppressed. When the amount of the proton conducting solvent is less than 0.1 wt%, the phase separation between the protonic quantum solvent and the nonpolar non-protonic solvent occurs, making it impossible to form a uniform solution. Further, by the phase separation phenomenon, the polar quantum solvent can not oxidize the acyl halide compound, and the phase-separated polar aprotic solvent acts as a defect in interfacial polymerization, which may cause the performance of the polyamide active layer to be significantly lowered have.
According to one embodiment of the present invention, the content of the polar protic solvent may be 0.0005 wt% or more and 0.03 wt% or less with respect to the organic solution. Specifically, according to one embodiment of the present invention, the content of the polar protic solvent may be 0.001 wt% or more and 0.03 wt% or less with respect to the organic solution. More specifically, according to one embodiment of the present invention, the content of the polar, quantum solvent may be 0.0015 wt% or more and 0.025 wt% or less with respect to the organic solution.
When the amount of the polar aprotic solvent is within the above range, the acyl halide compound is partially oxidized to maintain an excellent salt removal rate of the polyamide active layer and to increase the permeation flow rate.
If the content of the polar, quantitative solvent is less than the above range, the acyl halide compound can not be sufficiently oxidized and it is difficult to expect an effect of increasing the permeation flow rate. If the content of the polar, quantitative solvent exceeds the above range, the acyl halide compound may be excessively oxidized to make it difficult to form the polyamide active layer, or the salt removal rate may drop rapidly.
According to one embodiment of the present disclosure, the content ratio of the polar aprotic solvent to the polar aprotic solvent may be 6000: 1 to 20: 1. Specifically, according to one embodiment of the present disclosure, the content ratio of the polar aprotic solvent to the polar aprotic solvent may be 2000: 1 to 20: 1, or 1000: 1 to 20: 1. More specifically, according to one embodiment of the present disclosure, the ratio of the polar aprotic solvent to the polar aprotic solvent may be 500: 1 to 20: 1, or 50: 1 to 300: 1. Further, according to one embodiment of the present disclosure, the content ratio of the polar aprotic solvent to the polar aprotic solvent may be 100: 1 to 250: 1, or 100: 1 to 200: 1.
According to one embodiment of the present invention, the step of forming the polyamide active layer may be coating the organic solution on the aqueous solution layer, or immersing the aqueous solution layer in the organic solution.
According to one embodiment of the present invention, the porous support may be formed with a coating layer of a polymer material on a nonwoven fabric. Examples of the polymeric material include polymeric materials such as polysulfone, polyethersulfone, polycarbonate, polyethylene oxide, polyimide, polyetherimide, polyetheretherketone, polypropylene, polymethylpentene, polymethyl chloride and polyvinylidene fluoride Rides, and the like may be used, but the present invention is not limited thereto. Specifically, polysulfone may be used as the polymer material.
According to one embodiment of the present invention, the polyamide active layer can be formed through interfacial polymerization of the aqueous solution and the organic solution. When the aqueous solution and the organic solution are brought into contact with each other, an amine compound coated on the surface of the porous support reacts with an acyl halide compound to form a polyamide by interfacial polymerization and adsorbed on the microporous support to form a thin film. In the contact method, a polyamide active layer may be formed by a method such as dipping, spraying, or coating.
According to one embodiment of the present invention, a method of forming an aqueous solution layer containing an amine compound on the porous support is not particularly limited, and any method can be used as long as it is capable of forming an aqueous solution layer on a support. Specifically, a method of forming an aqueous solution layer containing an amine compound on the porous support includes spraying, coating, dipping, dropping, and the like.
At this time, the aqueous solution layer may be further subjected to a step of removing an aqueous solution containing an excess of the amine compound, if necessary. The aqueous solution layer formed on the porous support may be unevenly distributed when the aqueous solution present on the support is excessively large. If the aqueous solution is unevenly distributed, a non-uniform polyamide active layer may be formed by subsequent interfacial polymerization have. Therefore, it is preferable to remove the excess aqueous solution after forming the aqueous solution layer on the support. The removal of the excess aqueous solution is not particularly limited, but can be performed using, for example, a sponge, an air knife, nitrogen gas blowing, natural drying, or a compression roll.
According to one embodiment of the present invention, in the aqueous solution containing the amine compound, the amine compound is not limited as long as it is an amine compound used in the preparation of a water treatment separation membrane, but specific examples include m-phenylenediamine, p - phenylenediamine, 1,3,6-benzenetriamine, 4-chloro-1,3-phenylenediamine, 6-chloro-1,3-phenylenediamine, 3- Or a mixture thereof.
According to one embodiment of the present disclosure, the acyl halide compounds include, but are not limited to, for example, aromatic compounds having 2 to 3 carboxylic acid halides, such as trimethoyl chloride, isophthaloyl chlorides, Terephthaloyl chloride, and mixtures of at least one compound selected from the group consisting of terephthaloyl chloride.
According to one embodiment of the present invention, the water treatment separation membrane can be used as a microfiltration membrane, an ultrafiltration membrane, a nano filtration membrane or a reverse osmosis membrane, Can be used.
One embodiment of the present invention provides a water treatment separation membrane produced using the method for producing the water treatment separation membrane.
An embodiment of the present disclosure includes a porous support; And a polyamide active layer provided on the porous support, wherein the oxygen content of the polyamide active layer of the water treatment separation membrane is 20 wt% or more and 30 wt% or less.
According to one embodiment of the present invention, the oxygen content of the polyamide active layer may be 20 wt% or more and 25 wt% or less.
In the water treatment separator according to one embodiment of the present specification, the polyamide active layer may have a high oxygen content. Specifically, the organic solution for producing the polyamide active layer further includes a polar quantum solvent, so that the acyl halide compound can be partially oxidized. Accordingly, the polyamide active layer can exhibit a high oxygen content.
According to one embodiment of the present invention, the polyamide active layer may be formed by forming the polyamide active layer described above. Specifically, the polyamide active layer according to one embodiment of the present invention can achieve a high permeation flow rate while maintaining a high salt removal rate. As described above, in the interfacial polymerization for forming the polyamide active layer, the acyl halide compound is partially oxidized by the polar quantum solvent, and this can be represented by the high oxygen content of the polyamide active layer.
The oxygen content of the polyamide active layer may be a result of X-ray photoelectron spectroscopy (XPS). Specifically, the polyamide active layer sample was cut into a size of 2 cm x 2 cm, fixed on a sample holder, data was obtained using an XPS instrument according to K-Alpha standard operation, and then the oxygen content was measured using Avantage software (version 5.920) Respectively.
In addition, one embodiment of the present disclosure provides a water treatment module comprising at least one water treatment separation membrane.
The specific type 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 invention, other structures and manufacturing methods are not particularly limited and general means known in the art can be employed without limitation have.
On the other hand, the water treatment module according to one embodiment of the present invention has excellent salt removal rate and permeation flow rate, and is excellent in chemical stability, and thus can be used for water treatment devices such as household / industrial water purification devices, sewage treatment devices, have.
Hereinafter, the present invention will be described in detail by way of examples with reference to the drawings. However, the embodiments according to the present disclosure can be modified in various other forms, and the scope of the present specification is not construed as being limited to the embodiments described below. Embodiments of the present disclosure are provided to more fully describe the present disclosure to those of ordinary skill in the art.
[ Example One]
18% by weight of polysulfone solid was put into a solution of DMF (N, N-dimethylformamide) and melted at 80 ° C to 85 ° C for over 12 hours to obtain a uniform liquid phase. This solution was cast to a thickness of 150 탆 on a nonwoven fabric of 95 탆 to 100 탆 thickness made of polyester. The cast nonwoven fabric was then placed in water to form a porous polysulfone support.
An aqueous solution layer was formed by applying an aqueous solution containing 2.75 wt% of mepD (mPD) on the porous polysulfone support prepared as described above.
An organic solution was prepared by adding 0.25 g of a mixture of isophorone and 0.57 mg of methanol to 0.226 wt% of a trimesoyl chloride (TMC) solution using an ISOPar (Exxon) solvent, The resultant was applied on the aqueous solution layer and then dried to form a polyamide active layer to prepare a water treatment separation membrane.
[ Example 2]
Except that a mixed solution of 0.25 g of isophorone and 1.433 mg of methanol was added to 0.226 wt% of trimesoyl chloride (TMC) solution to prepare an organic solution. A separator was prepared.
The oxygen content of the polyamide active layer of the thus prepared water treatment separation membrane was 20.8 at%.
[ Example 3]
Except that an organic solution was prepared by adding 0.25 g of a mixture of isophorone and 2.866 mg of methanol to 0.226 wt% of a trimesoyl chloride (TMC) solution, A separator was prepared.
The oxygen content of the polyamide active layer of the thus prepared water treatment separation membrane was 23.3 at%.
[ Example 4]
Except that an organic solution was prepared by adding 0.25 g of a mixture of isophorone and 4.012 mg of methanol to 0.226 wt% of a trimesoyl chloride (TMC) solution, A separator was prepared.
The oxygen content of the polyamide active layer of the thus-prepared water treatment separation membrane was 24.9 at%.
[ Example 5]
Except that a mixed solution of 0.25 g of isophorone and 8.024 mg of methanol was added to 0.226 wt% of trimesoyl chloride (TMC) solution to prepare an organic solution. A separator was prepared.
The oxygen content of the polyamide active layer of the thus prepared water treatment separation membrane was 23.3 at%.
[ Comparative Example One]
A water treatment separation membrane was prepared in the same manner as in Example 1, except that a mixed solution of isophorine and methanol was added to a trimesoyl chloride (TMC) solution.
The oxygen content of the polyamide active layer of the water treatment separator thus prepared was 14.1 at%.
[ Comparative Example 2]
A water treatment membrane was prepared in the same manner as in Example 1, except that 0.25 g of isophorine was added to the trimethoyl chloride (TMC) solution.
The oxygen content of the polyamide active layer of the thus prepared water treatment separator was 16.4 at%.
[ Comparative Example 3]
Except that a mixed solution of 0.25 g of isophorone and 16.048 mg of methanol was added to 0.226 wt% of trimesoyl chloride (TMC) solution to prepare an organic solution. A separator was prepared.
[ Comparative Example 4]
Except that a mixed solution of 0.25 g of isophorone and 32.096 mg of methanol was added to 0.226 wt% of trimesoyl chloride (TMC) solution to prepare an organic solution. A separator was prepared.
In order to measure the salt rejection and the permeate flow rate (gfd) of the water treatment membranes prepared according to Examples 1 to 5 and the water treatment membranes prepared according to Comparative Examples 1 to 4, a plate type permeation cell, a high pressure pump, A water treatment module comprising a cooling device was used. The planar transmissive cell had a cross-flow structure with an effective permeable area of 28 cm 2. After the reverse osmosis membrane was installed in the permeable cell, the preliminary operation was performed for about 1 hour using the third distilled water to stabilize the evaluation equipment. After that, 250 ppm sodium chloride aqueous solution was operated at a flow rate of 60 psi and 4.5 L / min for about 1 hour to confirm that it stabilized, and then the amount of water permeated at 25 ° C. for 10 minutes was measured to calculate the flux , And the salt rejection rate was calculated by analyzing the salt concentration before and after the permeation using a conductivity meter.
The salt removal rate and permeation flow rate thus measured are shown in Table 1 below.
(wt%)
(wt%)
(%)
(GFD)
According to the above Table 1, it can be seen that the water treatment membrane according to the embodiment has a higher permeate flow rate than the comparative example. Further, it can be seen that the water treatment separation membrane according to the embodiment has a high permeation flow rate and a high salt removal rate of 90% or more.
Further, according to Comparative Examples 3 and 4, when an excessive amount of a polar protic solvent (methanol) was added, formation of the polyamide active layer was not smooth due to phase separation during interfacial polymerization, and methanol remained on the resulting polyamide active layer And the performance of the polyamide active layer is lowered.
In order to examine the compositional change of the water treatment separator according to the content of the polar aprotic solvent, the content of the polar aprotic solvent was fixed and the content of the polar aprotic solvent was changed as in the case of Examples 6 to 9, .
[ Example 6]
18% by weight of polysulfone solid was put into a solution of DMF (N, N-dimethylformamide) and melted at 80 ° C to 85 ° C for over 12 hours to obtain a uniform liquid phase. This solution was cast to a thickness of 150 탆 on a nonwoven fabric of 95 탆 to 100 탆 thickness made of polyester. The cast nonwoven fabric was then placed in water to form a porous polysulfone support.
An aqueous solution layer was formed by applying an aqueous solution containing 2.75 wt% of mepD (mPD) on the porous polysulfone support prepared as described above.
An organic solution was prepared by adding 0.125 g of a mixture of isophorone and 1.433 mg of methanol to 0.226 wt% of a trimesoyl chloride (TMC) solution using an ISOPar (Exxon) solvent, The resultant was applied on the aqueous solution layer and then dried to form a polyamide active layer to prepare a water treatment separation membrane.
[ Example 7]
A water treatment membrane was prepared in the same manner as in Example 6, except that 0.25 g of isophorone was added to the trimethoyl chloride (TMC) solution.
[ Example 8]
A water treatment membrane was prepared in the same manner as in Example 6, except that 0.375 g of isophorone was added to the trimethoyl chloride (TMC) solution.
[ Example 9]
A water treatment membrane was prepared in the same manner as in Example 6, except that 0.75 g of isophorone was added to the trimethoyl chloride (TMC) solution.
In order to measure the salt rejection and permeate flow rate (gfd) of the water treatment membranes prepared according to Examples 6 to 9, a water treatment module including a plate type permeation cell, a high pressure pump, a reservoir and a cooling device was used. The planar transmissive cell had a cross-flow structure with an effective permeable area of 28 cm 2. After the reverse osmosis membrane was installed in the permeable cell, the preliminary operation was performed for about 1 hour using the third distilled water to stabilize the evaluation equipment. After that, 250 ppm sodium chloride aqueous solution was operated at a flow rate of 60 psi and 4.5 L / min for about 1 hour to confirm that it stabilized, and then the amount of water permeated at 25 ° C. for 10 minutes was measured to calculate the flux , And the salt rejection rate was calculated by analyzing the salt concentration before and after the permeation using a conductivity meter.
The measured salt removal rate and permeate flow rate are shown in Table 2 below.
(wt%)
(wt%)
(%)
(GFD)
According to Table 2, it can be confirmed that as the content of the polar aprotic solvent increases with respect to the content of the polar, quantitative solvent, the salt removal rate decreases but the permeation flow increases. Based on the results shown in Table 2 above, the ratio of the polar aprotic solvent to the polar aprotic solvent for producing the water treatment separation membrane capable of exhibiting a salt removal rate of 90% or more and a permeation flow rate of 20 GFD or more is 100: 1 to 200 : May be one. However, the present invention is not limited thereto, and the optimum content can be derived based on the kind and content of the polar and quantitative solvent based on the above results.
Claims (11)
Preparing an aqueous solution containing an amine compound;
Preparing an organic solution comprising an acyl halide compound, a non-polar aprotic solvent, a polar aprotic solvent, and a polar quantum solvent;
Forming an aqueous solution layer on the porous support using the aqueous solution; And
And contacting the organic solution on the aqueous solution layer to form a polyamide active layer.
Wherein the step of preparing the organic solution comprises dissolving the acyl halide compound in the nonpolar nonionic solvent and then mixing the polar aprotic solvent and the polar protic solvent.
Wherein the polar aprotic solvent comprises at least one selected from the group consisting of a ketone solvent, an ester solvent, a cyan solvent, and a sulfoxide solvent.
Wherein the polar protic solvent comprises at least one selected from the group consisting of a carboxylic acid solvent, an alcohol solvent, water, and an amine-based solvent.
Wherein the content of the polar aprotic solvent is 0.1 wt% or more and 5 wt% or less with respect to the organic solution.
Wherein the content of the polar protic solvent is 0.0005 wt% or more and 0.02 wt% or less with respect to the organic solution.
Wherein the mass ratio of the polar aprotic solvent and the polar aprotic solvent is 6000: 1 to 20: 1.
Wherein the step of forming the polyamide active layer comprises coating the organic solution on the aqueous solution layer or immersing the aqueous solution layer in the organic solution.
A porous support; And a polyamide active layer provided on the porous support,
Wherein the polyamide active layer has an oxygen content of 20 at% or more and 30 at% or less.
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