KR101941767B1 - Renewable water-treatment membranes and method for manufacturing the same - Google Patents
Renewable water-treatment membranes and method for manufacturing the same Download PDFInfo
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- KR101941767B1 KR101941767B1 KR1020170024776A KR20170024776A KR101941767B1 KR 101941767 B1 KR101941767 B1 KR 101941767B1 KR 1020170024776 A KR1020170024776 A KR 1020170024776A KR 20170024776 A KR20170024776 A KR 20170024776A KR 101941767 B1 KR101941767 B1 KR 101941767B1
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
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- B01D67/0006—Organic membrane manufacture by chemical reactions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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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
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Abstract
The present invention relates to a separation membrane capable of adsorbing and separating contaminants such as heavy metals in polluted water and confirming the replacement timing of the separation membrane due to a change in fluorescence intensity. The separation membrane is regenerable, which can reuse the separation membrane without replacing the entire separation membrane.
Description
The present invention relates to a regenerable membrane for water treatment and a method for producing the same, and more particularly, to a membrane for water treatment which can be reused through restoration of a membrane function and a method for producing the same.
The water treatment method through the membrane is simple, small installation space and low energy consumption compared to the conventional physical, chemical, and biological water treatment methods, but has an advantage of excellent purification ability and its usage is gradually increasing.
However, there is a problem that when the water treatment is performed using the separation membrane, the pollutants to be removed accumulate on the surface of the separation membrane or the internal pores, resulting in a problem of fouling of the separation membrane, thereby shortening the life of the separation membrane.
In order to suppress the adhesion of the hydrophobic contaminants causing the separation membrane fouling, materials capable of decomposing hydrophilic materials or contaminants may be coated or grafted on the surface of the separation membrane, Attempts have been made to form membranes using mixed dope solutions.
Korean Patent Laid-Open Publication No. 10-2012-0048378 discloses a method of measuring the degree of contamination of a separation membrane by supporting fluorescent nanoparticles on a separation membrane, but merely confirming only the replacement time by fluorescence.
Such attempts may delay the membrane fouling rate and prolong the life of the membrane, but if the treatment limit of the chemical fouling functional material is reached, the entire membrane must be replaced in order to recover the membrane performance.
Further, in order for the functionalities desired to be imparted to be expressed in the separator to be developed, it is necessary to develop a suitable introduction process for each function, so that a large amount of manufacturing cost and development time are required, and development of technology is still required.
An object of the present invention is to provide a separation membrane capable of adsorbing and separating contaminants such as heavy metals in polluted water and confirming the replacement timing of the separation membrane due to a change in fluorescence intensity. It is still another object of the present invention to provide a regenerable separator capable of reusing a separator without replacing the whole of the separator and a method of manufacturing the same. Other objects and advantages of the present invention will become apparent from the following description. It is also to be easily understood that the objects and advantages of the present invention can be realized by a means or a method described in the claims and a combination thereof.
The present invention relates to a separator for solving the above problems and a method for producing the separator. A first aspect of the present invention is directed to the separation membrane, wherein the separation membrane comprises a separation membrane substrate; And fluorescent organic nanoparticles introduced into at least one side surface of the separation membrane substrate, wherein the fluorescent organic nanoparticles are capable of coordinate bonding with metal particles and quenching by binding. Here, the separation membrane substrate has a diene-dithiocyanurin linker complex introduced therein, and the fluorescent organic nanoparticles are introduced into the separation membrane substrate in a form bound to the linker complex.
According to a second aspect of the present invention, in the first aspect, the fluorescent organic nanoparticle is a macrocyclic compound selected from porphyrin, subphthalocyanine, phthalocyanine, and perylene, Substituted by one functional group, or unsubstituted.
In a third aspect of the present invention, in the first aspect, the linker complex comprises a diene-derived functional group introduced on at least one surface of the separation membrane, and a functional group derived from a dibenzene- Derived functional group introduced into at least one surface of the separation membrane, and a diene-derived functional group coupled with the functional group-derived functional group-derived functional group.
In a fourth aspect of the present invention, in the third aspect, the fluorescent organic nanoparticles are bound to a linker complex and introduced into a separation membrane, wherein the fluorescent organic nanoparticles are bound to a functional group derived from a pendant- will be.
In a fifth aspect of the present invention, in the fourth aspect, in the functional group-derived functional group, one end of the functional group is bonded to the fluorescent organic nanoparticle, and the other end of the functional group is coupled to maleimide so that maleimide functions as a pendant It is combined with the dienes introduced into the separator.
In a sixth aspect of the present invention, in the fourth or fifth aspect, the functional group derived from the dienes has one end of the functional group bonded to the separating membrane and the other end bonded to the furan, It is combined with Pandaism.
In a seventh aspect of the present invention, in any one of the first to sixth aspects, the separation membrane substrate includes at least one of a polymer material, an inorganic material, and a metal material.
In an eighth aspect of the present invention, in the ninth aspect, the polymer material is selected from the group consisting of polytetrafluoroethylene (PTFE), polyvinylidenefluoride (PVDF), polysulfone (PSF) Polyethersulfone (PES), Polyacrylonitrile (PAN), Polycarbonate (PC), Polyethylene (PE), Polypropylene (PP), Polyvinyl chloride (PVC) , Cellulose (cellulose), and cellulose acetate (cellulose acetate).
The present invention also provides a process for producing a water treatment separator. A ninth aspect of the present invention relates to the above method, and includes the following steps (S10) to (S30).
(S10) introducing a diene-based functional group into at least one surface of the separation membrane;
(S20) introducing a functional group originating in a pendant group into the fluorescent organic nanoparticles; And
(S30) The step of reacting the result of step (S10) with the result of step (S20) to couple a functional group derived from a diene and a functional group derived from a polyene to form a coupling.
The tenth aspect of the present invention is the method as set forth in the ninth aspect, wherein the step (S30) is performed by heat treating the separation membrane at a temperature ranging from 20 캜 to 70 캜.
The present invention also provides a method of regenerating a water treatment separator. An eleventh aspect of the present invention relates to the above method, and includes the following steps (S100) to (S300).
(S100) a step of filtering the water containing contaminants including heavy metals into any one of the water treatment membranes of the above-mentioned side to attach contaminants to the fluorescent organic nanoparticles;
(S200) heat-treating the separation membrane having the contaminant attached thereto to dissociate the coupling between the diene-derived functional group and the polyene-derived functional group of the diene-dithiane linker complex; And
(S300), fluorescent organic nanoparticles to which a functional group derived from thienylene is bonded are added to recombine functional groups derived from dienes and functional groups derived from polyenes.
In a twelfth aspect of the present invention, in the eleventh aspect, in the step (S200), the separation membrane is heated to a temperature of 80 to 200 ° C.
A thirteenth aspect of the present invention resides in the eleventh aspect or the twelfth aspect, wherein the step (S200) is performed by a Deels-Elder reverse reaction.
According to a fourteenth aspect of the present invention, in any one of the eleventh to thirteenth aspects, before performing the step (S200), if the intensity of fluorescence of the separation membrane is measured (S250) Further comprising the step of determining the membrane separation.
In the present invention, it is possible to separate contaminants such as heavy metals in contaminated water by the fluorescent organic nanoparticles introduced into the separator, and at the same time, it is possible to confirm the replacement timing of the separator through the quenching effect of the fluorescent organic nanoparticles. In addition, the organic nanoparticles combined with heavy metals can be removed by a simple heat treatment process, so that the separation membrane can be used for regeneration.
BRIEF DESCRIPTION OF THE DRAWINGS The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this application, illustrate preferred embodiments of the invention and, together with the description of the invention, It is not interpreted. On the other hand, the shape, size, scale or ratio of the elements in the drawings incorporated herein can be exaggerated to emphasize a clearer description.
1 is a schematic perspective view of a water treatment separator according to an embodiment of the present invention.
FIG. 2 shows FT-IR as a result of phthalocyanine synthesis.
FIG. 3 schematically illustrates a method of manufacturing a separation membrane for water treatment according to an embodiment of the present invention.
FIG. 4 shows the state of the surface of the separation membrane modified by the introduction of fluorescent organic nanoparticles on the surface of the separation membrane through ATR-IR.
FIG. 5 shows changes in fluorescence properties of a PTFE separator into which fluorescent organic nanoparticles are introduced according to an embodiment of the present invention.
Figure 6 shows the attachment and desorption process of phthalocyanine particles through the ATR FT-IR spectra.
FIG. 7 shows changes in fluorescence properties due to attachment and desorption of phthalocyanine particles through fluorescence spectra.
FIG. 8 is a diagram illustrating a structure of a separation membrane according to a specific embodiment of the present invention and a mechanism by which contaminants are removed using the separation membrane.
Hereinafter, embodiments of the present invention will be described in detail. Prior to this, terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms, and the inventor should appropriately interpret the concepts of the terms appropriately It should be interpreted in accordance with the meaning and concept consistent with the technical idea of the present invention based on the principle that it can be defined. Therefore, the constitutions described in the embodiments described herein are merely the most preferred embodiments of the present invention, and are not intended to represent all of the technical ideas of the present invention. Therefore, various equivalents which can be substituted at the time of application It should be understood that variations can be made.
The present invention relates to a water treatment separator. The water treatment separator may be applied to one or more of, for example, ultrafiltration and microfiltration. In the present invention, the water-treatment separation membrane has fluorescent organic nanoparticles introduced into at least one surface thereof. In addition, the fluorescent organic nanoparticles are capable of coordinating with metal particles, and have quenching characteristics in which fluorescence is weakened or fluorescence is canceled by binding with metal particles. In one specific embodiment of the present invention, the fluorescent organic nanoparticles may be introduced into the separation membrane in a form combined with the linker complex introduced into the separation membrane.
Next, various specific embodiments of the present invention will be described with reference to the accompanying drawings.
1 is a schematic perspective view of a water treatment separator according to an embodiment of the present invention. 1, a regenerable
In one specific embodiment of the present invention, the separator substrate may be applied to any material applied in the art without limitation. Non-limiting examples thereof include any one of a polymeric material, an inorganic material, and a metallic material, or a mixture of two or more thereof. In one specific embodiment of the present invention, the polymer material is selected from the group consisting of polytetrafluoroethylene (PTFE), polyvinylidenefluoride (PVDF), polysulfone (PSF), polyethersulfone PES), polyacrylonitrile (PAN), polycarbonate (PC), polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), cellulose And cellulose acetate. ≪ RTI ID = 0.0 > [0040] < / RTI > The polymer material is preferably at least one selected from the group consisting of polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), polysulfone (PSF), and polyethersulfone . ≪ / RTI >
The inorganic material that can be used as the separator substrate may be at least one of aluminum oxide (Alumina), silicon oxide, and titanium oxide, or a mixture thereof may be used. Stainless steel, and palladium alloy, or a mixture thereof may be used.
In addition, the above-described material may be used as the separator substrate, or the surface of the separator substrate may be modified to at least one selected from the group consisting of OH, -NH2, -CN, -CO-, -COOH, and -CONH-.
In the present invention, the fluorescent organic nanoparticles are macrocyclic compounds having at least one selected from porphyrin, subphthalocyanine, phthalocyanine, and perylene. In one specific embodiment of the present invention, the macrocyclic compound may be substituted with at least one of the functional groups, or may be unsubstituted. In one specific embodiment of the present invention, the macrocyclic compound may be nitrophthalocyanine, which is a tetrameric form of aminophthalonitrile.
These fluorescent organic nanoparticles are in a form capable of coordinating with the metal and / or metal ion on the core portion of the molecular structure. Further, it exhibits a characteristic of emitting fluorescence, and such fluorescence emission characteristic is canceled by binding with metal and / or metal ion. Therefore, it is useful to remove the contaminant heavy metal ion by the introduction of the fluorescent organic nanoparticles and to detect the change of the optical characteristics of the separation membrane and to confirm the replacement time of the separation membrane.
In a specific embodiment of the present invention, the metal or metal ion may be a heavy metal or an ion thereof. The heavy metal is a metal having a specific gravity of about 4.0 or more, or 5.0 or more. Non-limiting examples of such heavy metals include aluminum (Al), arsenic (As), barium (Ba), uranium (U), bismuth (Bi), thallium (Ti), cesium (Cs), antimony (Sb) Co, beryllium, manganese, chromium, iron, nickel, copper, zinc, cadmium, tin, Hg), lead (Pb), and the like.
In the present invention, such fluorescent organic nanoparticles can be introduced into the separation membrane through a linker. In one specific embodiment of the present invention, the linker of the present invention may be in the form of a diene-pendantene linker complex. That is, in the separation membrane according to the present invention, the separation membrane substrate is provided with a diene-dithiocyanurate linker complex on one surface or both surfaces thereof, and the fluorescent organic nanoparticles are introduced into the separation membrane in the form of binding to the linker complex.
The dienes applicable to the present invention are materials having a structure in the order of a double bond-single bond-double bond, and materials having an s-cis diene form can be used without limitation. Butadiene, cyclopentadiene, pyrrole, and furan, or a mixture thereof may be used. In one specific embodiment of the present invention, the dienes may be furan.
Also, the pendant diene may be coupled with a diene to form a ring, and the pendant diene applicable to the present invention may be any material including a double bond or a triple bond without limitation , And non-limiting examples include at least one selected from the group consisting of acrylonitrile, quinone, maleic anhydride maleimide, and the like. In one specific embodiment of the present invention, the pendant may be maleimide.
In one specific embodiment of the present invention, the diene-dithiane linker complex is a product of Diels-Alder reaction of dienes and pseudoadenes, May be in covalent bond form.
The Diels-Alder reaction is a reaction that can control the reaction of the reaction by changing the temperature, pressure, and concentration of the substance in a thermodynamically equilibrium state.
The Diels-Alder reaction is an organic chemical reaction of conjugated dienes and pseudoenes, in which a mixture of conjugated dienes and p-dienes is charged with energy such as heat , The reaction proceeds regularly and cyclic hexane is formed. The reverse reaction thereof is also dissociated into a mixture of conjugated dienes and pendants in which the cyclic cyclohexane is dissociated.
The present invention relates to a separation membrane in which the fluorescent organic nanoparticles are introduced into the surface of the separation membrane for water treatment by the diene-pendantyne linker complex formed by the above-described Diels-Alder reaction, Playback can be used.
More specifically, heating the surface of the water treatment separator with contaminants to a high temperature progresses a retro Diels-Alder reaction, thereby dissociating the diene-chidane bond. Such a bond dissociation can easily remove contaminants, and the functionality of the separator can be restored by forming a linker complex by bonding a pure diene-pendant at a proper temperature.
The diene-dithiane linker complex which can be applied to the present invention includes a diene-based functional group introduced into one or both surfaces of a separation membrane substrate and a functional group derived from a polybenzene bonded to the diene-based functional group can do. At this time, the fluorescent organic nanoparticles are combined with functional groups originating from a polythiophene and introduced into the separation membrane.
According to another embodiment, the diene-dithiincylene linker complex may be prepared by reacting a functional group-derived functional group derived from a polyfunctional monomer introduced into one side or both sides of a separation membrane with a functional group derived from a diene- . At this time, the fluorescent organic nanoparticles are combined with functional groups derived from dienes and introduced into the separation membrane.
In one specific embodiment of the present invention, the diene-based functional group introduced into the separating membrane substrate or the functional group-derived functional group derived from the polybenzylene sulfonic acid introduced into the separating membrane substrate is independently 0.1 to 30 parts by weight per 100 parts by weight of the separating membrane substrate , Preferably 1 to 10 parts by weight.
In one embodiment of the present invention, the functional group-derived functional group may be one in which one end of the functional group is bonded to the fluorescent organic nanoparticle and the other end is coupled to maleimide. At this time, maleimide acts as a pendantiene to form a linker complex bonded with a diene introduced into the separation membrane, for example, furan.
Next, a method for producing a water treatment membrane and a method for regenerating a water treatment membrane will be described. In the same structure as the above-described water treatment separator in the following description, if it is determined that repetition of the description may unnecessarily obscure the gist of the present invention, the detailed description may be omitted, but the same applies to be.
A method of manufacturing a regenerable water treatment separator according to another embodiment of the present invention includes the following steps (S10) to (S30):
(S10) introducing a diene-based functional group into at least one surface of the separation membrane;
(S20) introducing a functional group originating in a pendant group into the fluorescent organic nanoparticles; And
(S30) The step of reacting the result of step (S10) with the result of step (S20) to bind the functional group derived from the diene and the functional group derived from the polyene to introduce the fluorescent organic nanoparticles into the separation membrane through the linker complex.
In the step (S20), the fluorescent organic nanoparticle and the functional group-derived functional group may be directly bonded to the fluorescent organic nanoparticle in the step of introducing the functional group-derived functional group into the fluorescent organic nanoparticle. Or a substituent that allows the binding of the two components to the terminal of at least one of the functional group or the fluorescent organic nanoparticle in the pendantene can be introduced and the two components can be bonded through such a substituent. In a specific embodiment of the present invention, the substituent may include, for example, an amine group, an alcohol group, a carboxyl group, a thiol group and the like. For example, a substituent group containing an amine group may be introduced at the terminal of the fluorescent organic nanoparticle to allow the amine group to bind to the functional group derived from the pendant. The binding by substituent introduction is not limited to the above-mentioned contents, and it is obvious that any substituent capable of binding the fluorescent organic nanoparticle of the present invention with the functional group derived from the pendant is usable.
At this time, the linker complex of (S30) may be formed by a Diels-Alder reaction of a functional group derived from a diene and a functional group derived from a polyene, 40 to < RTI ID = 0.0 > 60 C. < / RTI >
In a specific embodiment of the present invention, a method of introducing a fluorescent dye into a separation membrane, combining fluorescent nanocrystalline particles and a dienes, and complexing a dienes and a pendant to form a linker complex, It is also possible to prepare a separation membrane in the order that the organic particles are introduced into the separation membrane.
Further, in another specific embodiment of the present invention, in the method for producing a water-separating membrane, after introducing the diene-dithiocyanurate linker complex on at least one surface of the separation membrane, It is also possible to carry out the method by combining with a sieve.
The present invention also provides a method for regenerating a separation membrane for water treatment according to the present invention. The reproducing method may include the following steps (S100) to (S300).
(S100) preparing a separation membrane having contaminants attached to the fluorescent organic nanoparticles;
(S200) heat-treating the separation membrane having the contaminant attached thereto to dissociate the coupling between the functional group derived from the dienes and the functional group derived from the polyenes of the linker complex; And
(S300) a step of adding a fluorescent organic nanoparticle to which a functional group derived from a thienylene derivative is bonded to form a linker complex.
The above method assumes that the functional group derived from the dienes in the linker complex is bonded to the separation membrane and the fluorescent organic nanoparticles are bonded to the functional group derived from the polymer. In addition, by performing the above-described step (S200), the fluorescent dyes coupled with the fluorescent organic nanoparticles are removed from the separation membrane, and the contaminants are attached to the fluorescent organic nanoparticles (S200) . On the other hand, the functional group derived from the dendritic polymer added in the step (S300) is attached with the fluorescent organic nanoparticles. In this case, the fluorescent organic nanoparticles are in a state in which the fluorescent characteristic is maintained as no contaminants are attached. On the other hand, the fluorescent organic nanoparticles may be recovered after the step S200 and recovered after removing contaminants.
If the functional group of the linker complex is bound to the separation membrane and the separation membrane in which the fluorescent organic nanoparticles are bonded to the functional group derived from the dienes is regenerated (S200), the functional group derived from the pendant is introduced into the separation membrane And the functional group derived from the dienes is recovered (step S300), so that the fluorescent organic nanoparticles to which the functional group derived from the dienes are bonded can be added to reproduce the linker complex.
The water-treated separation membrane is subjected to a heat treatment to dissociate the coupling between the functional group derived from the dienes and the functional group derived from the polyenes of the diene-dithienyl chain linker complex to remove the contaminants, The reaction for disassociating the linker complex may be variously applied, but it may preferably be a retro Diels-Alder reaction. At this time, the temperature for the heat treatment is 80 to 200 ° C, preferably 100 to 150 ° C, and the retro Diels-Alder reaction does not proceed outside the temperature range.
Hereinafter, the present invention will be described in detail with reference to the following examples. However, the embodiments according to the present invention can be modified in various other forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. Embodiments of the present invention are provided to provide a more complete understanding of the present invention to those skilled in the art.
[Example 1]
Polytetrafluoroethylene (PTFE) Membrane Substrate To introduce the furan functionality onto the substrate surface, the polytetrafluoroethylene (PTFE) membrane substrate was first exposed to hydrazine vapor and ultraviolet light of 264 nm was applied for 48 hours at an output of 100 W To obtain a polytetrafluoroethylene (PTFE) membrane substrate modified with an amine group. Thereafter, a polytetrafluoroethylene (PTFE) membrane base material modified with an amine group was impregnated into a solution of furfuryl glycidyl ether, and then reacted at 60 ° C. to finally obtain a polytetrafluoroethylene (PTFE) membrane substrate .
At this time, it was confirmed through the XPS surface oxygen atom ratio analysis that 2 to 20 parts by weight of furan functional groups were introduced into 100 parts by weight of the polytetrafluoroethylene (PTFE) membrane base material modified with amine groups.
Meanwhile, FIG. 4 shows the result of confirming whether or not the surface of the separation membrane is reformed through ATR FT-IR. In the green graph of FIG. 4, it was confirmed that the carbon double bond strength of furan was exhibited by FT-IR of the separation membrane into which the furan functional group was introduced.
Next, a maleimide group-bonded phthalocyanine was prepared using 4-aminophthalonitrile containing a nitro group as a precursor. 4-aminophthalonitrile was dissolved in propanol, and then ketoxime was added thereto to prepare a tetrafunctional nitrophthalocyanine. Next, the prepared tetrameric form of nitrophthalocyanine is dissolved in dimethylformamide in a nitrogen atmosphere, sodium sulfide hydrate is added thereto, and the terminal of the phthalocyanine is modified into an amine group. Next, the prepared aminophthalocyanine was dissolved in tetrahydrofuran together with triethylamine, and then the maleimide derivative was covalently bonded thereto to finally obtain a phthalocyanine (Pc-Maleimide) having a maleimide substituent .
FIG. 2 shows the result of FT-IR analysis for phthalocyanine synthesis steps. Through this, an amino group is introduced into 4-nitropthalonitrile, and it is confirmed that phthalocyanine having a maleimide substituent group is formed by bonding with maleimide.
Phthalocyanine-maleimide (Pc-Maleimide) was dissolved in a toluene organic solvent at a concentration of 5%. The solution was impregnated with a polytetrafluoroethylene (PTFE) membrane base material modified with a furan group, and then phthalocyanine was introduced into polytetrafluoroethylene (PTFE) through a Diels-Alder reaction between furan and maleimide at about 60 ° C to obtain phthalocyanine -PTFE (phthalocyanine-PTFE) separation membrane was prepared.
At this time, the prepared phthalocyanine-PTFE (phthalocyanine-PTFE) separator contained 1 to 10 parts by weight of Pc-Maleimide based on 100 parts by weight of the polytetrafluoroethylene (PTFE) separator.
FIG. 3 schematically illustrates a method of manufacturing a separation membrane according to a specific embodiment of the present invention.
[Performance evaluation]
Experiment to evaluate change of fluorescence property of membrane
The separation membrane prepared in Example 1 was used to confirm the removal of heavy metals and the change of fluorescent properties. A heavy metal aqueous solution containing 0.001 to 0.01 part by weight of chromium 6-valent ions and iron-trivalent ions was prepared, and the fluorescence properties of the surface of the separation membrane were observed in the range of 300 to 800 nm while permeating the phthalocyanine-PTFE separation membrane for 30 minutes.
5 is a graph showing changes in fluorescence properties of the separation membrane prepared in Example 1. FIG. 5 (a) and (b) show Cr (VI), and (c) and (d) show the fluorescence scavenging ability against Fe (III). It was confirmed that the fluorescence properties of the B-band region of 350-500 nm and the Q-band region of 700-800 nm were erased with the permeation time of the heavy metal ion-containing raw water.
Evaluation of regeneration ability of membrane
The separation membrane prepared in Example 1 was impregnated with a toluene solvent, and the Diels-Elder reverse reaction was carried out at 150 ° C to remove phthalocyanine adhered to the surface of the separation membrane. Diels-Alder reaction was carried out in the same manner as in Example 1 to introduce phthalocyanine into the PTFE separation membrane where phthalocyanine was desorbed, thereby preparing a separation membrane having phthalocyanine surface bound thereto. The surface attachment and desorption reaction of phthalocyanine on the PTFE membrane were repeated three times to confirm reproducibility.
Fig. 6 is an FT-IR spectra result showing the attachment and desorption process of phthalocyanine of the separation membrane produced in Example 1. Fig. According to this, it can be confirmed that the intensity of the portion indicated by hue is changed by the introduction and removal of phthalocyanine. That is, the C = O, N-H, and C-N IR bands of phthalocyanine are observed in the corresponding part, and these IR bands mostly disappear in the retro Diels-Alder reaction.
Fig. 7 shows results of confirming the fluorescence spectra. According to the results, it is possible to confirm the change of fluorescence properties due to attachment and desorption of phthalocyanine. Fluorescence properties are confirmed when Pc is introduced, but fluorescence disappears after retro Diels-Alder reaction.
10: Membrane substrate
20: Diene-derived functional group
30: Functional mechanism derived from spermine
40: diene-dithiane linker complex
50: Fluorescent nanoparticles
100: Regenerable membrane for water treatment
Claims (15)
And fluorescent organic nanoparticles introduced into at least one surface of the separator substrate,
The fluorescent organic nanoparticles are capable of coordinating with metal particles and quenching by binding,
The separator substrate is introduced with a diene-dithiocyanurate linker complex,
Wherein the fluorescent organic nanoparticles are introduced into the separator substrate in a form bound to the linker complex.
Wherein the fluorescent organic nanoparticle is a macrocyclic compound selected from the group consisting of porphyrin, subphthalocyanine, phthalocyanine, and perylene, and the macrocyclic compound is at least one of a functional group, Separation membrane for water treatment.
Wherein the linker complex comprises a diene-derived functional group introduced into at least one surface of the separation membrane, and a functional group derived from a polyene copolymer coupled with the functional group derived from the diene polymer, Derived functional group, and a diene-based functional group coupled with the functional group-derived functional group.
Wherein the fluorescent organic nanoparticles are bonded to the linker complex and introduced into the separation membrane, wherein the fluorescent organic nanoparticles are combined with the functional group derived from the pendant organoleptic of the linker complex.
The functional group-derived functional group is characterized in that one end of the functional group is bonded to the fluorescent organic nanoparticle and the other end of the functional group is coupled to maleimide so that the maleimide is bonded to the diene introduced into the separation membrane by acting as a pendant Which can be regenerated.
The diene-based functional group is characterized in that one end of the functional group is bonded to the separation membrane, and the other end of the functional group is bonded to furan, so that furan acts as a diene and is bonded to the pendant.
Wherein the separation membrane substrate comprises at least one of a polymer material, an inorganic material, and a metal material.
The polymeric material may be selected from the group consisting of polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), polysulfone (PSF), polyethersulfone (PES), polyacrylonitrile (PAN), polycarbonate (PC), polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), cellulosic and cellulose acetate And at least one selected from the group consisting of:
(S10) introducing a diene-based functional group into at least one surface of the separation membrane;
(S20) introducing a functional group originating in a pendant group into the fluorescent organic nanoparticles; And
(S30) The step of reacting the result of step (S10) with the result of step (S20) to couple a functional group derived from a diene and a functional group derived from a polyene to form a coupling.
Wherein the step (S30) is performed by heat treating the separation membrane at a temperature ranging from 20 to 70 占 폚.
(S200) heat-treating the separation membrane having the contaminant attached thereto to dissociate the coupling between the diene-derived functional group and the polyene-derived functional group of the diene-dithiane linker complex; And
(S300) a fluorescent organic nanoparticle to which a functional group derived from a polythiophene is bonded is added to recombine the functional group derived from the dienes and the functional group derived from the polythienes;
Wherein the water separator is a water separator.
(S200), the separation membrane is subjected to a heat treatment such that the separation membrane has a temperature of 80 ° C to 200 ° C.
Wherein the step (S200) comprises a reverse elder reaction.
The method of claim 1, further comprising, before performing the step (S200), measuring intensity of fluorescence of the separation membrane (S250) and determining the separation membrane number if the intensity of the fluorescence does not reach the preset strength.
Priority Applications (2)
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| KR101159076B1 (en) | 2010-11-05 | 2012-07-03 | 한국화학연구원 | Measuring method of fouling of membrane containing fluorescent nano particle |
| JP2014118551A (en) | 2012-12-19 | 2014-06-30 | Tohoku Univ | Porous structure, oxygen sensor and separation membrane using the same, and method for producing porous structure |
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| KR101711049B1 (en) * | 2015-07-30 | 2017-03-13 | 서울대학교산학협력단 | Renewable water-treatment membranes and method for manufacturing the same |
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| KR101159076B1 (en) | 2010-11-05 | 2012-07-03 | 한국화학연구원 | Measuring method of fouling of membrane containing fluorescent nano particle |
| JP2014118551A (en) | 2012-12-19 | 2014-06-30 | Tohoku Univ | Porous structure, oxygen sensor and separation membrane using the same, and method for producing porous structure |
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| Hui Xu, et al., "Recent progress in metal-organic complexes for optoelectronic applications", Chemical Society Reviews, 2014, 43, pp. 3259-3302* |
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