KR101789529B1 - Nanofiltration Membrane for water treatment containing Porous carbon structure using polymers of intrinsic microporosity and preperation method thereof - Google Patents

Abstract

The present invention relates to a water treatment membrane comprising a porous carbon structure made of an intrinsic porous polymer and a method for producing the same. The water treatment membrane comprising the porous carbon structure having the intrinsic porous polymer according to the present invention carbonizes the porous polymer film made of the intrinsic porous polymer to form a porous carbon structure having a porous structure with a high surface area and a good water permeability , It exhibits excellent water permeability and salt removal rate and can be usefully used for reverse osmosis filtration or nanofiltration in the main water treatment process.

Description

[0001] The present invention relates to a membrane for water treatment comprising a porous carbon structure made of an intrinsic porous polymer and a method for producing the same,

The present invention relates to a water treatment membrane comprising a porous carbon structure made of an intrinsic porous polymer and a method for producing the same.

As the global water shortage problem becomes more serious, technologies and industries that desalinate seawater as the most abundant resource on the planet and produce it as usable water are attracting attention. Among various water treatment techniques, the technology based on a polymer membrane has been studied for its merits such as ease and efficiency (see Non-Patent Document 1).

This polymer membrane-based water treatment technology can be classified into MF (Microfiltration) membrane, UF (Ultrafiltration) membrane, NF (Nanofiltration) membrane and RO (reverse osmosis) membrane depending on its application and membrane size. MF membranes and UF membranes are mainly used to purify colloidal dispersions, MF membranes can float bacteria and suspended solids, and UF membranes can contain viruses that are slightly smaller. In addition, the NF membrane and the RO membrane are mainly used to filter ions dissolved in an aqueous solution. It is known that this principle can be controlled by adjusting the size of the pores in the film and the charge of the surface.

In addition to the above-mentioned water shortage problem, the energy problem is also one of recent big issues. Therefore, many studies have been conducted to develop a technique of obtaining a large amount of fresh water at a low energy (pressure) or the same pressure in the course of desalination using seawater.

Among them, high permeability-polymer membranes containing carbon nanomaterials are attracting attention. It has been reported that minority channels of carbon nanomaterials push water molecules out of the pressurized system when they enter the water system, thereby increasing the permeability (see Non-Patent Documents 2 to 4).

However, these studies have a problem in that it is difficult to make a large area, and there is a limitation in reducing the diameter and pore size of the carbon nanomaterial, and ions in the aqueous solution can not be removed without using the polymer medium.

Therefore, the inventors of the present invention have found that a water treatment membrane comprising a porous carbon structure having an intrinsic porous polymer according to the present invention has a high surface area and exhibits excellent water permeability and salt removal rate. Therefore, in the main water treatment process, reverse osmosis filtration or nano filtration The present invention has been accomplished on the basis of these findings.

Korean Patent No. 10-1485867

Energy Environ. Sci., 2011, Vol.4, pp.1946-1971. Science, 2006, Vol.312, pp.1003-1004. Science, 2006, Vol.312, pp.1034-1037. Science, 2012, Vol.335, pp.413-414.

It is an object of the present invention to provide a water treatment membrane wherein the intrinsic porous polymer comprises a carbonized porous carbon structure.

Another object of the present invention is to provide a method for producing the water treatment membrane.

In order to achieve the above object,

The present invention provides a water treatment film comprising a porous carbon structure in which a homopolymer or a copolymer of a compound represented by the following formula (1), or a mixture containing at least one thereof, is carbonized:

[Chemical Formula 1]

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The present invention also provides a process for producing a film (step 1) using a homopolymer or a copolymer of a compound represented by the following formula (1), or a mixture containing at least one of these polymers; And

And carbonizing the film produced in the step 1 to prepare a water treatment film containing the porous carbon structure (step 2).

The water treatment membrane comprising the porous carbon structure having the intrinsic porous polymer according to the present invention carbonizes the porous polymer film made of the intrinsic porous polymer to form a porous carbon structure having a porous structure with a high surface area and a good water permeability , It exhibits excellent water permeability and salt removal rate and can be usefully used for reverse osmosis filtration or nanofiltration in the main water treatment process.

Fig. 1 is a photograph of the membrane prepared in Comparative Example 1, Example 1 and Example 2 according to the present invention.
FIG. 2A is a graph showing the results of ultrapure water permeation test according to the carbonization ratio of Comparative Example 1 according to the present invention. FIG. 2B is a graph showing the permeation rate of the membrane of Comparative Example 1 according to the carbonization rate upon permeation of MgSO ₄ solution (2,000 ppm) FIG. 2C is a graph showing the results of the water permeation and salt removal experiments according to the membrane of Comparative Example 1 with a carbonization rate of 37.5% at the time of permeation of MgSO ₄ solution (2,000 ppm) and the membrane thickness of Example 1 according to the present invention The results are shown.
FIG. 3A is a graphical representation of the production process of a carbonized porous carbon structure (PC-PIM-1, Example 2) having a surface of the present invention treated with oxygen plasma, FIG. 3B is a graph showing the process of Comparative Example 2 of the present invention, FIG. 3C is a graph showing the results of measurement of penetration of ultrapure water, water permeation, and salt removal ratio of each membrane according to Example 1 and Example 2 with a carbonization rate of 60%, and FIG. 3C is a graph showing the results of measurement of bovine serum albumin (1 g / L) And FIG. 3B is a graph showing time-dependent normalized water permeation change of each membrane according to Example 1 and Example 2 with a thickness of 20 μm and a carbonization rate of 60% in Comparative example 2, examples 1 and 2 of the film is shown having the optimized remove MgSO ₄ and the number of transmission performance graphs.

Hereinafter, the present invention will be described in detail.

The present invention provides a water treatment film comprising a porous carbon structure in which a homopolymer or copolymer of a compound represented by the following general formula (1), or a mixture containing at least one thereof, is carbonized.

[Chemical Formula 1]

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Hereinafter, a water treatment membrane comprising a carbonized porous carbon structure in which a homopolymer or a copolymer of the compound represented by the formula (1) according to the present invention or a mixture containing at least one thereof is carbonized will be described in detail.

In the water treatment membrane comprising the intrinsically porous carbon-based porous structured polymer according to the present invention, the homopolymer or copolymer of the compound represented by the formula (1), or a mixture containing at least one thereof, it means. Polymers of Intrinsic Microporosity (PIM) have a skeleton of a twisted structure and are not densely packed in a solid phase, resulting in microporosity (microporosity) on the surface of the polymer.

According to the definition of IUPAC, the porous carbon material may be a micropore (pore size <2 nm), a mesopore (2 nm <pore size <50 nm, and macropores (pore size> 50 nm). The porous carbon structure including the intrinsic porous polymer according to the present invention may have micropores and mesopores, Of micropores.

Accordingly, the water treatment membrane containing the porous carbon structure having the intrinsic porous polymer according to the present invention has micropores of 2 nm or less, so that ions dissolved in the aqueous solution can be removed.

Further, in the water treatment membrane comprising the porous carbon structure having the intrinsic porous polymer according to the present invention, the porous carbon structure in which the intrinsic porous polymer is carbonized has a microporous structure by the intrinsic porous polymer, The surface area is increased by carbonization. The carbonized porous carbon structure according to the present invention may have a surface area of not less than about 300 m ² / g, but is not limited thereto. Preferably from 300 m ² / g to 2000 m ² / g, and more preferably from 300 m ² / g to 1500 m ² / g.
The degree of carbonization of the water treatment film is preferably 30 to 65%.

In addition, the porous carbon structure in which the intrinsic porous polymer is carbonized may have a film form, and the film form is not particularly limited, but may be a porous carbon film having a thickness of several micrometers to several hundreds of micrometers.

In addition, in the water treatment membrane comprising the porous carbon structure having the intrinsic porous polymer according to the present invention, the pore may be modified to a minor water surface through which the water permeability can be increased through the carbonization process, Can be used for water treatment membranes.

In addition, the water treatment membrane comprising the porous carbonaceous structure having the intrinsic porous polymer according to the present invention may be subjected to oxygen plasma treatment on the surface of the membrane.

Therefore, the water treatment membrane comprising the porous carbon structure having the intrinsic porous polymer according to the present invention has a high surface area due to the structural and morphological characteristics and carbonization as described above, so that the water permeability can be increased, Since the effect of increasing the salt removal rate by increasing the contact area with the salt aqueous solution can be obtained, it can be usefully used for reverse osmosis filtration or nanofiltration in the main water treatment process.

As a result of evaluating the water permeability of the water treatment membrane including the porous carbon structure having the intrinsic porous polymer according to the present invention, it was found that the water treatment membrane of Example 1 in which the carbonization was performed, as compared with Comparative Example 1 in which no carbonization was performed, It can be seen that both permeation and water permeation exhibit remarkably excellent permeability. Example 2 in which oxygen plasma treatment was performed on the surface of the water treatment membrane of Example 1 in which carbonization was carried out shows a comparison between the same thickness and carbonization ratio, showing ultrapure water permeability and water permeability than Example 2 in which oxygen plasma treatment was performed have. Comparing Example 1 with Comparative Example 2 which is a conventional water treatment film, when the thickness of Example 1 was 30 占 퐉 or less, the water permeability and ultrapure water permeability were remarkably superior to Comparative Example 2 .

On the other hand, in the case of the salt removal rate, the salt removal rate tends to decrease as the water permeability increases. It can be seen that the water treatment membranes of Examples 1 and 2 according to the present invention exhibit high water permeability and exhibit a high salt removal rate and the water permeation performance and the salt removal rate are lower than those of Comparative Example 2 which is a conventionally used water treatment membrane All of which are remarkably excellent.

As shown in FIG. 3B, when the membranes of Examples 1 and 2 according to the present invention had a thickness of 20 占 퐉 and a carbonization ratio of 60%, they were significantly superior to Comparative Example 1 (NF2A) Ultrapure water permeation and water permeation performance. It is seen that the performance is more than 2 times in the case of the example 1 and 3 times or more in the case of the case of the example 2. In the case of Example 2, it can be seen that the permeation performance and permeation performance of ultrapure water of about 1.5 times higher than that of Example 1 are shown.

As shown in FIG. 3C and FIG. 3D, when the membranes of Examples 1 and 2 according to the present invention and the membranes of Comparative Example 2 were compared with each other in terms of optimum salt removal rate and water treatment capability, It can be seen that the membranes of Examples 1 and 2 according to the present invention exhibit remarkably superior water permeability than the membrane of Example 2, and in particular, the membrane of Example 2 exhibits water permeability three times or more.

Therefore, the carbonized porous carbon structure (C-PIM-1) film of Example 1 according to the present invention and the carbonized porous carbon structure (PC-PIM-1) (Comparative Example 1) and the conventionally used water treatment film (Comparative Example 2), it exhibits a high water permeability and is excellent in the salt removal rate, and thus can be effectively used as a water treatment film.

As shown in FIG. 2C, it can be seen that as the thickness of the membrane of Example 1 according to the present invention increases, the salt removal rate slightly increases and the water permeability decreases. As a result, it can be seen that the salt removal rate tends to decrease as the water permeability of Example 1 according to the present invention increases.

Generally, as the water permeability increases, an inverse phenomenon is observed in which the salt flux increases and the salt removal rate decreases accordingly. The reason why the water treatment film containing the porous carbon structure having the intrinsic porous polymer according to the present invention does not show the conventional phenomenon is that the nano sized pores inside the membrane during the carbonization process are water It is expected that it will have permeable surface properties.

Further, as a result of measuring water permeation characteristics of the water-treating membrane containing the carbonized porous carbon structure according to the present invention, it was found that the porous carbon structure having the inherent porous polymer according to the present invention It can be seen that the water permeation property is improved as the carbonization ratio is increased in both case of permeation of pure water or permeation of water containing salt.

This can be an indirect evidence that the nanotube or nano-sized pores inside the membrane become carbonized and the water permeability increases.

The present invention also provides a process for producing a film (step 1) using a homopolymer or a copolymer of a compound represented by the following formula (1), or a mixture containing at least one of these polymers; And

And carbonizing the film produced in the step 1 to prepare a water treatment film containing the porous carbon structure (step 2).

[Chemical Formula 1]

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Hereinafter, a method for producing a water treatment membrane comprising a porous carbon structure in which a homopolymer or a copolymer of the compound represented by the formula (1) according to the present invention or a mixture containing at least one thereof is carbonized will be described in detail.

Herein, the homopolymer or copolymer of the compound represented by the formula (1), or a mixture containing at least one thereof, refers to an intrinsic porous polymer.

The method for producing the water treatment film is not particularly limited, but can be carried out using a film forming method.

In the method for manufacturing a water treatment membrane comprising the porous carbon structure having the intrinsic porous polymer according to the present invention, the step 1 may be a homopolymer or a copolymer of the compound represented by the general formula (1) And the film is prepared using the mixture to be contained.

Specifically, step 1 is a step (step a) of coating a substrate with a homopolymer or copolymer of the compound represented by the formula (1), or a mixture solution containing one or more of these polymers; And

And drying the coated solution in step (a) to produce a film (step (b)).

Herein, the homopolymer or copolymer of the compound represented by the formula (1), or a mixture containing at least one thereof, refers to an intrinsic porous polymer. Specifically, the intrinsic porous polymer in step (a) has a skeleton of a twisted structure, so that the polymer is not densely packed in a solid phase, resulting in microporosity (microporosity) on the surface of the polymer.

In addition, the intrinsic porous polymer solution in step a is obtained by dissolving the intrinsic porous polymer in a solvent. The solvent which can be used is not particularly limited as long as a polymer solution can be prepared, but chloroform, tetrahydrofuran, dichlorobenzene, dimethylacetamide, dimethylsulfoxide, dimethylformamide, etc. may be used alone or in combination , Preferably chloroform may be used.

Further, the number average molecular weight of the intrinsically porous polymer is preferably in the range of 1,000 to 1,000,000. When the molecular weight is less than 1,000, there is a problem that the viscosity is low and the film is broken when forming the film. When the molecular weight is more than 1,000,000, the solubility of the film in the solvent is low.

In addition, the concentration of the intrinsic porous polymer solution is not particularly limited, but may be adjusted to 0.3 - 2 wt% although the molecular weight is different. When the content is less than 0.3% by weight, there is a problem that the film thickness is thin and the shape is not maintained in the course of film production and carbonization. When the content is more than 2% by weight, the thickness of the resulting film becomes too thick, have. Therefore, by adjusting the concentration range as described above, it is possible to produce a porous carbon structure having high surface area and water permeability.

Furthermore, although the substrate of step a is not particularly limited, a glass substrate, a SiO ₂ / Si substrate, a polymer substrate such as polycarbonate and polyimide may be used, and a glass substrate may be preferably used.

The evaporation is not particularly limited, but may be carried out at room temperature under an atmosphere.

In the method for manufacturing a water treatment membrane comprising the porous carbon structure having the intrinsic porous polymer according to the present invention, the step 2 may include carbonizing the intrinsic porous polymer film produced in the step 1, Thereby producing a water treatment film.

The pore surface of the porous carbon structure in which the intrinsic porous polymer is carbonized through the carbonization is modified to a minority surface capable of increasing water permeability.

At this time, the carbonization is performed by heating the intrinsic porous polymer film in an oxygen deficiency state. The conditions for carrying out the carbonization include, but are not limited to, an atmosphere of an inert gas such as argon or nitrogen; An inert gas atmosphere containing one or more gases such as hydrogen; Vacuum atmosphere; Or under at least one of these atmospheres, preferably under a gaseous atmosphere in which hydrogen and nitrogen are mixed.

The carbonization is not particularly limited, but is preferably performed at 400 ° C or higher, more preferably 400 ° C to 3000 ° C, and most preferably 400 ° C to 1800 ° C. If the carbonization temperature is less than 400 ° C, carbonization is difficult and amorphous carbon is present in a large amount, so that water permeation characteristics of the carbon structure may be lowered. If the temperature is higher than 3000 ° C, carbon volatilization may occur.

Further, the carbonization time is not particularly limited, but may be 30 minutes to 20 hours.

The carbonization is carried out by carrying out a step of carbonizing at 400 to 1800 占 폚 under the above-mentioned atmospheric condition (first carbonizing step), carbonizing at a temperature of 1800 占 폚 to 3000 占 폚 under the above-mentioned atmospheric condition ) Can be performed. By performing the first carbonization process and the second carbonization process as described above, a porous carbon structure having improved quality can be manufactured.

Further, the method for producing the water treatment membrane may further include performing oxygen plasma treatment on the surface of the water treatment membrane after the step 2 is performed.

The water treatment membrane prepared by the method for producing a water treatment membrane containing the porous carbon structure having the intrinsic porous polymer according to the present invention has a high surface area due to its structural and morphological characteristics and carbonization, And it is possible to increase the salt removal rate by increasing the contact area with the salt aqueous solution. Therefore, it can be effectively used for reverse osmosis filtration or nanofiltration in the main water treatment process.

Further, the present invention provides a water treatment method comprising the step of using a water treatment membrane comprising a carbonized porous carbon structure according to the present invention.

Since the water treatment membrane containing the carbonized porous carbon structure according to the present invention has excellent water permeability and is excellent in salt removal rate and can be usefully used for water treatment, the water treatment method including the step of using the same can also be used for water treatment have.

Hereinafter, examples and experimental examples of the present invention will be described in detail.

However, the following Examples and Experimental Examples are merely illustrative of the present invention, and the present invention is not limited to the following Examples and Experimental Examples.

< Manufacturing example  1> Intrinsic Microporosity Polymers (Polymers of Intrinsic Microporosity; PIM )

After the internal water and air of the two-necked round flask (250 ml) were removed, the flask was maintained in a nitrogen atmosphere and 5.5 ', 6,6'-tetrahydroxy-3,3,3'1,1'-spiro-by-indan (TTSBI, 5.5 ', 6,6'- tetrahydroxy-3,3,3', 3'-tetramethyl-1,1'-spirobiindan) (3.40 g), K 2 CO 3 (4.14 g), tetrafluorophthalonitrile (TFTPN) (2.00 g) and dimethylformamide (DMF) (70 ml) were added, and polymerization was carried out at 55 ° C for 72 hours. After termination of the reaction, it slowly precipitated in water and filtered. The filtrate was dried in a vacuum drier at 60 ° C. for 24 hours, dissolved in tetrahydrofuran (THF) and reprecipitated twice using methanol. The final product was vacuum dried to obtain a yellowish intrinsic microporous polymer (PIM-1) (4.05 g). GPC (Gel Permeation Chromatography) measurement showed values of M _n = 50,000 and PDI (Polydispersity Index) 1.7.

< Example  1 > Carbonized Porous Carbon Structure (C- PIM -1) membranes

Step 1: A porous carbon structure ( PIM -1) membranes

The intrinsic microporous polymer (PIM-1) obtained in Preparation Example 1 was diluted in chloroform in an amount of 0.3 to 2% by weight and injected into a glass Petri dish while filtering impurities with a 1 μm syringe filter. The solvent was slowly evaporated in an atmosphere of air for two days, and then the film was separated from the glass Petri dishes using distilled water. And dried in a vacuum drier adjusted to 100 DEG C for 24 hours. The dried film was immersed in methanol for one day and then dried in a vacuum drier adjusted to 100 DEG C for 24 hours. A porous carbon structure (PIM-1) film having a thickness of 10 to 100 μm was prepared as described above.

Step 2: The porous carbon structure (C- PIM -1) membrane carbonization

The PIM-1 film prepared in the above Step 1 was sandwiched between a synthetic graphite fixing device or a silicon wafer and placed in a high-temperature furnace and heated at a temperature raising rate of 5 ° C / min from 1100 to 1300 ° C The carbonized porous carbon structure (C-PIM-1) of various carbonization ratios was prepared by performing carbonization for 0 to 4 hours.

< Example  2> When the surface is oxygen ₂ ) plasma  Preparation of Treated Carbonated Porous Carbon Structure (PC-PIM-1) Membrane

Both surfaces of the carbonized porous carbon structure (C-PIM-1) film prepared in Example 1 were subjected to oxygen (O ₂ ) plasma treatment. The instrument used for the plasma treatment consists of a parallel electrode operated at a radio-frequency of 13.56 MHz.

The carbonized porous carbon structure (C-PIM-1) membrane was placed on the feed electrode under an argon / oxygen (Ar / O ₂ ) flow (71/29 vol% and 30 sccm). The time and power of the oxygen plasma treatment for the preparation of carbonized porous carbon structures with surface-treated plasma are 30 seconds and 185 W, respectively. The plasma treatment was performed at a treatment time of 10 to 300 seconds and a treatment power of 50 to 185 W, but no significant performance change was observed.

< Comparative Example  1> Porous carbon structure ( PIM -1) membranes

The polymer (PIM-1) having the intrinsic micropores obtained in Preparation Example 1 was diluted in chloroform in an amount of 0.3 to 2% by weight and injected into a glass Petri dish while filtering impurities with a 1 μm syringe filter. The solvent was slowly evaporated in an atmosphere of air for two days, and then the film was separated from the glass Petri dishes using distilled water. And dried in a vacuum drier adjusted to 100 DEG C for 24 hours. The dried film was immersed in methanol for one day and then dried in a vacuum drier adjusted to 100 DEG C for 24 hours. A porous carbon structure (PIM-1) film having a thickness of 10 to 100 μm was prepared as described above.

< Comparative Example  2> NF membrane ( Nanofiltration )

The NF membrane was modeled by NF2A manufactured by Hydranautics.

< Experimental Example  1> Water permeability  Characteristic and Salt Removal Rate Evaluation

In order to evaluate the water permeation characteristics of the porous carbon structure membrane according to the present invention, the carbonized porous carbon structure (C-PIM-1) membrane prepared in Example 1 and the membrane prepared in Example 2 having different thicknesses and carbonization ratios the surface of the oxygen (O ₂₎ plasma treating the carbonized porous carbon structure (PC-PIM-1) prepared in Comparative example 1 and the film porous carbon structure (PIM-1) membrane and NF membrane (nanofiltration) according to Comparative example 2 Pure water flux experiments were conducted.

In order to evaluate the characteristics of removing the ions in the aqueous solution of the porous carbon structure membrane according to the present invention (salt removal), the carbonized porous carbon structure (C-PIM- (PIM-1) membrane prepared in Comparative Example 1 and the carbonized porous carbon structure (PC-PIM-1) membrane in which the surface prepared in Example 2 was treated with oxygen (O ₂ ) A 2000 ppm MgSO ₄ aqueous solution permeation experiment was performed on the NF membrane (nanofiltration) of Comparative Example 2.

In order to evaluate the water permeation characteristics of the carbonized porous carbon structural body membrane according to the present invention, the carbonized porous carbon structural body (C-PIM-1) prepared in Example 1 having different thicknesses and carbonization rates ) Membrane and the carbonized porous carbon structure (PC-PIM-1) membrane in which the surface prepared in Example 2 was subjected to oxygen (O ₂ ) plasma treatment and the porous carbon structure (PIM-1) membrane prepared in Comparative Example 1 Water permeation experiments were performed with the NF membrane (nanofiltration) of Example 2.

The results of the ultrapure water permeation, salt removal rate and water permeation test are shown in the following Tables 1, 2 and 3.

membrane Film thickness
(μm) Carbonization rate
(%) Ultrapure water permeation
(LMH bar ^-1 ) Water permeability
(LMH bar ^-1 ) Salt removal rate
(%) Comparative Example 2 - - 4.66 ± 0.20 3.32 ± 0.11 76.86 + 1.59 Comparative Example 1 20 - 0.31 ± 0.01 0.13 ± 0.00 91.18 ± 0.18 " 30 - 0.23 + 0.02 0.12 ± 0.00 91.41 + - 0.23 " 37.5 - 0.18 + 0.03 0.09 ± 0.01 91.78 ± 0.15 " 40 - 0.13 ± 0.00 0.09 ± 0.00 91.42 + 0.33 " 50 - 0.12 + - 0.01 0.09 ± 0.00 92.16 ± 0.29 " 60 - 0.11 + - 0.01 0.09 ± 0.01 93.39 + 0.17 " 70 - 0.10 0.00 0.09 ± 0.00 93.69 + 0.21 Example 1 30 40 4.85 ± 0.17 3.51 + - 0.16 82.69 ± 1.91 " " 47.5 5.32 ± 0.05 3.73 ± 0.05 82.94 + - 0.68 " " 50 5.65 ± 0.19 3.90 ± 0.05 81.54 ± 0.59 " " 60 6.43 + 0.09 4.45 ± 0.02 78.76 ± 1.21 " 20 37.5 7.08 ± 0.24 4.91 ± 0.05 79.29 + - 0.58 " 30 " 4.80 ± 0.17 3.30 ± 0.07 83.40 0.35 " 35 " 4.09 + 0.03 2.76 ± 0.09 83.64 ± 0.45 " 40 " 3.47 ± 0.04 2.38 + 0.11 83.64 ± 0.53 " 45 " 3.12 ± 0.03 2.20 ± 0.07 79.29 + - 0.58 " 50 " 2.88 + 0.02 1.96 ± 0.01 84.70 + 0.04 " 55 " 2.64 ± 0.09 1.82 + - 0.01 84.65 + 0.24 " 70 " 2.06 ± 0.06 1.47 ± 0.01 85.76 ± 0.16 " 20 60 10.57 + - 0.42 7.74 ± 0.18 78.58 + - 0.46 Example 2 30 40 7.04 + 0.08 5.74 + - 0.10 79.60 ± 0.82 " " 47.5 8.38 ± 0.07 6.33 ± 0.03 78.94 ± 0.52 " " 50 8.82 + 0.14 6.54 + 0.02 77.38 + - 0.24 " " 60 10.79 ± 0.24 7.95 + - 0.01 76.51 + - 1.18 " 20 37.5 10.40 0.26 7.36 ± 0.13 75.91 + - 0.62 " 30 " 6.98 + 0.11 4.91 ± 0.05 78.50 + - 0.41 " 35 " 5.92 + 0.04 4.22 + 0.07 80.94 + 0.17 " 40 " 5.08 + 0.04 3.71 ± 0.07 83.03 ± 0.19 " 45 " 4.55 + 0.09 3.35 + 0.02 83.55 + 0.29 " 50 " 4.19 + 0.04 3.07 ± 0.05 83.85 + 0.26 " 55 " 3.80 ± 0.05 2.76 ± 0.06 84.03 ± 0.19 " 70 " 2.95 ± 0.05 2.21 ± 0.05 85.20 ± 0.51 " 20 60 15.43 + - 0.45 13.30 ± 0.57 77.37 ± 0.36

As shown in Table 1, it was found that the water treatment membrane of Example 1 in which carbonization was carried out exhibited remarkably excellent permeability in both ultrapure water permeation and water permeation as compared with Comparative Example 1 in which carbonization was not carried out. Example 2 in which oxygen plasma treatment was performed on the surface of the water treatment membrane of Example 1 in which carbonization was carried out shows a comparison between the same thickness and carbonization ratio, showing ultrapure water permeability and water permeability than Example 2 in which oxygen plasma treatment was performed have. Comparing Example 1 with Comparative Example 2 which is a conventional water treatment film, when the thickness of Example 1 was 30 占 퐉 or less, the water permeability and ultrapure water permeability were remarkably superior to Comparative Example 2 .

On the other hand, in the case of the salt removal rate, the salt removal rate tends to decrease as the water permeability increases. It can be seen that the water treatment membranes of Examples 1 and 2 according to the present invention exhibit high water permeability and exhibit a high salt removal rate and the water permeation performance and the salt removal rate are lower than those of Comparative Example 2 which is a conventionally used water treatment membrane All of which are remarkably excellent.

As shown in FIG. 2C, it can be seen that as the thickness of the membrane of Example 1 according to the present invention increases, the salt removal rate slightly increases and the water permeability decreases. As a result, it can be seen that the salt removal rate tends to decrease as the water permeability of Example 1 according to the present invention increases.

As shown in FIG. 3B, when the membranes of Examples 1 and 2 according to the present invention had a thickness of 20 占 퐉 and a carbonization ratio of 60%, they were significantly superior to Comparative Example 1 (NF2A) Ultrapure water permeation and water permeation performance. It is seen that the performance is more than 2 times in the case of the example 1 and 3 times or more in the case of the case of the example 2. In the case of Example 2, it can be seen that the permeation performance and permeation performance of ultrapure water of about 1.5 times higher than that of Example 1 are shown.

As shown in FIG. 3C and FIG. 3D, when the membranes of Examples 1 and 2 according to the present invention and the membranes of Comparative Example 2 were compared with each other in terms of optimum salt removal rate and water treatment capability, It can be seen that the membranes of Examples 1 and 2 according to the present invention exhibit remarkably superior water permeability than the membrane of Example 2, and in particular, the membrane of Example 2 exhibits water permeability three times or more.

Therefore, the carbonized porous carbon structure (C-PIM-1) film of Example 1 according to the present invention and the carbonized porous carbon structure (PC-PIM-1) (Comparative Example 1) and the conventionally used water treatment film (Comparative Example 2), it exhibits a high water permeability and is excellent in the salt removal rate, and thus can be effectively used as a water treatment film.

Claims (13)

1. A water treatment membrane comprising a porous carbon structure in which a homopolymer or copolymer of a compound represented by the following formula (1), or a mixture containing at least one thereof, is carbonized:
[Chemical Formula 1]

(In the above formula (1), X is

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The method according to claim 1,
Wherein the water treatment membrane is for reverse osmosis filtration or for nanofiltration.
The method according to claim 1,
Wherein the water treatment film has a surface area of 300 m ² / g or more and 2000 m ² / g or less.
The method according to claim 1,
Wherein the water treatment film has a degree of carbonization of 30 to 65%.
The method according to claim 1,
Wherein the water permeability of the water treatment membrane is 1-6 LMH bar ^-1 .
The method according to claim 1,
Wherein the salt removal rate of the water treatment membrane is 70 - 100%.
The method according to claim 1,
Wherein the surface of the water treatment film is subjected to oxygen plasma treatment.
A process for producing a film using a homopolymer or a copolymer of a compound represented by the following formula (1), or a mixture containing at least one of these polymers (step 1); And
(2) carbonizing the film produced in the step (1) to prepare a water treatment film containing the porous carbon structure (step 2). The method for producing a water treatment film according to claim 1,
[Chemical Formula 1]

(In the above formula (1), X is the same as defined in the above formula (1)).
9. The method of claim 8,
Step 1 is a step (a) of coating a substrate with a homopolymer or copolymer of the compound represented by the formula (1), or a mixture solution containing one or more of these polymers; And
And drying the coated solution in the step (a) to produce a film (step (b)).
10. The method of claim 9,
Wherein the concentration of the homopolymer or copolymer of the compound represented by Formula 1 or the mixture solution containing at least one of the polymers is 0.3 to 2% by weight.
9. The method of claim 8,
Wherein the carbonization in step 2 is performed at a temperature of 400 to 3000 ° C.
9. The method of claim 8,
And performing oxygen plasma treatment on the surface of the water treatment membrane after the step 2 is performed.
A water treatment method comprising the use of the water treatment membrane of claim 1.

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