KR20190117025A - Water desalination and water purification using diatom and cucurbituril - Google Patents

Abstract

The present invention relates to a method for water desalination and purification using diatoms and cucurbiturils. According to the present invention, a diatom-cucurbituril complex prepared by modifying the surface of diatoms with a silane compound and linking cucurbiturils to an amine group of the silane compound via a non-covalent linkage can significantly increase water purifying efficiency, and can facilitate the acquisition of purified water from high-concentration of salt or various pollutants through the application to seawater and wastewater. Especially, the method can be helpfully utilized in removing organic dyes from wastewater, removing dissolved heavy metals from water, removing radioactive isotopes from radioactive wastes, deodorizing and decolorizing livestock wastewater and steel mill wastewater, and the like.

Description

Water desalination and water purification using diatom and cucurbituril

The present invention relates to a desalination and purification process using diatoms and cooker bituril.

Diatoms are unicellular algae that are distributed in various sizes from 2 μm to 2 mm and are representative phytoplankton commonly found on Earth. Diatoms account for 20-25% of the total primary production of land and 40% of marine biomass production, and have played an important role in ecosystems as marine producers for millions of years. In addition, diatomaceous earth is a natural siliceous material which is a main component of diatomaceous cell membrane, and is known as bio-silica because it is calcined at 450 ° C. and composed of silica-rich silica on the surface. The size of bio-silica is about 10-20 μm. Recently, studies are being actively conducted to utilize diatoms or diatomaceous earth as inorganic materials, bioenvironmental materials, nanoengineered materials or industrial application materials.

Cookerbituril was first reported by R. Behrend, E. Meyer and F. Rusche in 1905. In 1981, W. Mock and co-workers reported that It was found that the monomer is a large ring compound in which a ring is formed to have a chemical formula of C ₃₆ H ₃₆ N ₂₄ O ₁₂ , and its structure was confirmed by X-ray diffraction (J. Am. Chem. Soc.1981). , 103, 7367). They named the compound cucurbituril [6]. Later, in 2000, Kim and Kim and co-workers improved the synthesis method of cookerbituril [6] to synthesize and isolate not only cookerbituril [6] but also the homologue, cucurbituril [n] (n = 5, 7, 8). Each structure was confirmed by X-ray diffraction (J. Am. Chem. Soc. 2000, 122, 540).

Cooker bituril is a macrocyclic molecular compound with lipophilic pupils and a hydrophilic inlet on both sides. Therefore, cucurbituril has a lipophilic interaction in the cavity and hydrogen bonds, polar interactions, and cation-polar interactions at the two upper and lower inlets of six carbonyl groups, which are highly non-covalent with various kinds of compounds. It shows the effect of inclusion through binding. In particular, a compound having a very stable non-covalent bond to a compound having a functional group, such as amino groups, carboxylic acids, and the like, due to this property has been continuously studied in the development of various drug delivery systems.

On the other hand, many countries, including underdeveloped countries, have a lot of interest in the development of water purification technology, and recently, water purification technology incorporating nanomaterials is in the spotlight. However, the conventional technology has a problem in that the efficiency is low because of the relatively low water purification efficiency, and thus, it is necessary to develop a new technology, and desalination and water purification techniques through grafting cucurbituril to diatoms have not been reported to date.

Republic of Korea Patent Registration No. 10-1464226 (2014.11.17 registration)

SUMMARY OF THE INVENTION An object of the present invention is to provide a composite comprising diatom and cucurbituril modified with a silane compound, a composition for desalination or water purification using the same, a membrane filter for desalination or water purification, a desalination or water purification treatment device, and a desalination or water purification treatment method. Is in.

In order to achieve the above object, the present invention is a diatom (Diatom) modified with a silane compound; And a cucurbituril, which is represented by Formula 1 below, and binds to an amine group of the silane compound.

[Formula 1]

In Formula 1 n is an integer of 5 to 8.

In addition, the present invention provides a composition for desalination or water purification comprising the complex.

In addition, the present invention provides a membrane filter for desalination or water purification comprising the composite.

In addition, the present invention provides a desalination or water purification treatment apparatus comprising the complex.

In addition, the present invention provides a wastewater purification treatment method comprising the; treating the complex to wastewater to remove contaminants.

In addition, the present invention provides a desalination treatment method comprising the; treating the complex to a solution containing salt.

According to the present invention, a diatom-cookerbituril complex prepared by modifying a diatom surface with a silane compound and non-covalently bonding a cucurbituril to an amine group of the silane compound can significantly increase the water purification efficiency, and is applied to seawater and wastewater. Thus, fresh water can be easily obtained from a high concentration of salt or various contaminants. In particular, it can be usefully used for removing organic dyes in wastewater, removing heavy metals dissolved in water, removing radioisotopes in radioactive waste, deodorizing and decolorizing livestock wastewater and steel mill wastewater.

1 shows a diatom-cookerbituril complex in which a cucurbituril is bonded to a diatom modified with an amine group-containing silane compound and a dye removal mechanism by the complex.
Figure 2 is a result of comparing the dye removal efficiency according to the concentration of cucurbituril 6 (CB [6]).
Figure 3 is a result of comparing the dye removal efficiency according to the cucurbituril type (CB [5-8]).
4 shows diatom alone (D), cucurbituril 6 (CB [6]), diatom-cookerbituril6 (D-CB [6]), diatom (DA) modified with an amine group-containing silane compound and amine group-containing silane It is a result of comparing the dye removal efficiency by diatom-cookerbituril 6 (DA-CB [6]) modified with the compound.
FIG. 5 shows the results of dye removal efficiency according to diatom and cucurbituril type (DA-CB [5-8]) modified with amine group-containing silane compound.
6 is a result of confirming the mixed dye removal efficiency by diatom-cookerbituril 8 (DA-CB [8]).
7 shows the dye removal efficiency of the filter to which diatom-cookerbituril 8 (DA-CB [8]) is applied.

The inventors of the present invention treated the diatom surface with APTES to modify the amine group, and non-covalently bonded to the cucurbituril to the amine group to prepare a diatom-cookerbituril complex, wherein the diatom-cookerbituril complex is about 10-40 times compared to the single material. The present invention was completed by confirming that the water purification efficiency can be applied to desalination and wastewater purification significantly.

The present invention is a diatom (Diatom) modified with a silane compound; And a cucurbituril, which is represented by Formula 1 below, and binds to an amine group of the silane compound.

[Formula 1]

In Formula 1 n is an integer of 5 to 8.

The silane compound may be represented by the following Chemical Formula 2, but is not limited thereto.

[Formula 2]

Wherein R ¹ to R ³ may each be the same or different, either C1 to C4 alkyl or C1 to C4 alkoxy, R ⁴ is amino (C1 to C10) alkyl, 3- (2-amino ( C1 to C4) alkylamino) (C1 to C4) alkyl or 3- [2- (2-amino (C1 to C4) alkylamino) (C1 to C4) alkylamino] (C1 to C4) alkyl.

More preferably. The silane compound is (3-aminopropyl) triethoxysilane (APTES), (3-aminopropyl) trimethoxysilane, (1-aminomethyl) (1-aminomethyl) triethoxysilane, (2-aminoethyl) triethoxysilane, (4-aminobutyl) triethoxysilane ((5-aminopentyl) triethoxysilane), (6-aminohexyl) triethoxysilane, 3-aminopropyl (diethoxy) methylsilane ( 3-aminopropyl (diethoxy) methylsilane), N- [3- (trimethoxysilyl) propyl] ethylenediamine (N- [3- (trimethoxysilyl) propyl] ethylenediamine), [3- (2-aminoethylamino) propyl] Consisting of trimethoxysilane ([3- (2-aminoethylamino) propyl] trimethoxysilane (AEAPTMS) and 3-[(trimethoxysilyl) propyl] diethylenetriamine (3 [(trimethoxysilyl) propyl] diethylenetriamine (TMPTA) But which it may have one or more selected from, specifies that not limited to this.

The amine group of the silane compound may be bonded non-covalently with cucurbituril.

In addition, the present invention provides a composition for desalination or water purification comprising the complex.

The composition may be directly applied to wastewater containing seawater or pollutants, and may be applied to membrane filter membranes, columns, gels, and the like to be used in desalination or water purification treatment.

In addition, the present invention provides a membrane filter for desalination or water purification comprising the composite. The membrane filter may be selected from the group consisting of a reverse osmosis filter, a hollow fiber membrane filter, an ultrafiltration membrane filter, a nano- and micro-filtration membrane filter, but is not limited thereto.

The present invention also provides a desalination or water purification treatment apparatus comprising the complex.

In addition, the present invention provides a wastewater purification treatment method comprising the; treating the complex to wastewater to remove contaminants.

The pollutant may be selected from the group consisting of organic dyes, heavy metals and radioisotopes, but is not limited thereto.

In addition, the present invention provides a desalination treatment method comprising the; treating the complex to a solution containing salt.

Hereinafter, the present invention will be described in more detail with reference to Examples. These examples are only for illustrating the present invention in more detail, it will be apparent to those skilled in the art that the scope of the present invention is not limited by these examples in accordance with the gist of the present invention. .

Example  1: Diatom-Cookerbituril Composite Preparation

As shown in Chemical Formula 1 and Table 1 below, cucurbituril (CB) is a macrocyclic compound in which 5-8 monomers are combined to form a CB [5], CB [6], CB [7], and CB [8]. , 4 homologues exist. Cookerbituril has a lipophilic pupil and a hydrophilic inlet on both sides, so lipophilic interactions occur within the pupil, and hydrogen bonds, polar interactions, and cation-polar interactions at the upper and lower entrances of the carbonyl group, respectively. This makes it possible to exhibit an inclusion effect through a very stable non-covalent bond with various kinds of compounds. In particular, it is possible to form a complex through a non-covalent bond that is very stable with respect to a compound having a functional group such as an amino group, carboxylic acid.

[Formula 1]

In the present invention, as shown in Figure 1, diatoms (3-aminopropyl) triethoxysilane ((3-aminopropyl) triethoxysilane (APTES)) by treating the diatom surface was modified with an amine group (amine group). Briefly, 1 g of diatomaceous earth powder was immersed in distilled water for 30 minutes, and then immersed in 70% EtOH and 99% EtOH for 30 minutes sequentially, and then completely dried using Vaccum. The dried 500 mg of diatomaceous earth was put into 80 ml of 98% EtOH solution, 2.4 ml of APTES was added and reacted at room temperature for 4 hours. After washing with distilled water, the final concentration was stored to make 50 mg / ml.

Diatom-cookerbituril (DA-CB [X], X = 5-8) complexes were prepared by treating various types of cooker bituril to the diatoms modified with the amine group-containing silane compound, respectively. The cucurbituril CB [5] (ca. 545198), CB [6] (ca. 94544), CB [7] (ca. 545201) and CB [8] (ca. 545228) used in the present invention are obtained from Sigma-Aldrich. It was purchased and prepared using a CB [X] solution of 0.001 g / ml concentration using mineral water. To prepare the complex, 1 ml (0.001 mg / ml) of CB [X] was added to 9 ml (50 mg / ml) of diatom modified with the amine group-containing silane compound, and reacted at room temperature for 20 minutes. . The prepared composite used the required dose according to the experiment.

Example 2: Dye Removal Efficiency Assay

1) Dye removal effect of cucurbituril

Using the same type of cucurbituril CB [6] and preparing a cucurbituril solution at various concentration conditions as shown in FIG. 2, each solution was added to 1 ml of Trypan Blue solution (Abs: -0.95) and 4 The reaction was carried out for a time. Dye removal efficiency by cucurbituril was analyzed using a spectrophotometer (Biochrom Libra S22 UV / Vis).

As a result, referring to Figure 2, it was confirmed that sedimentation in trypan blue is improved as the concentration of cucurbituril CB [6] increases.

Next, the type of cucurbituril was changed to CB [5], CB [6], CB [7], CB [8], and a cucurbituril solution was prepared at the same concentration (0.001 g / ml), and then each solution was It was added to 1 ml of Pan Blue solution (Abs: -0.95) and reacted for 4 hours to analyze dye removal efficiency by cucurbituril.

As a result, referring to FIG. 3, the dye removal efficiency of CB [8] was the best among various CB types, and it was confirmed that the dye removal reaction was completed within about 2 hours.

2) Dye Removal Effect of Diatom-Cookerbituril Complex Modified with Amine Group-Containing Silane Compound

Diatom alone (D) (50 mg / ml), cucurbituril 6 (CB [6]) (0.001 mg / ml), diatom-cookerbituril6 (D-CB [6]) (50 mg / ml D, 0.001 mg / ml CB [6]), diatom (DA) modified with amine group-containing silane compound (50 mg / ml), diatom-cookerbituryl6 (DA-CB [6]) modified with amine group-containing silane compound (50 mg / ml DA, 0.001 mg / ml CB [6]) solutions, respectively, Each solution was added to 1 ml of Trypan Blue solution (Abs: -0.95) and reacted for 4 hours to analyze dye removal efficiency.

As a result, referring to FIG. 4, the dye removal efficiency was significantly lower in the case of diatom (D), and in the case of the diatom (DA) modified with the amine group-containing silane compound, the dye removal efficiency was about twice as high as that of the diatom alone. The improvement was confirmed. In addition, it was confirmed that DA-CB [6] complexes in which cucurbituril was bonded to diatoms modified with amine group-containing silane compounds showed about 10 times better dye removal efficiency than other materials.

3) Dye removal effect according to diatom and cucurbituril type modified with amine group-containing silane compound

DA-CB [X] (50 mg / ml DA, 0.001 mg / ml CB [X]) complexes were prepared with different CB types in diatoms modified with amine group-containing silane compounds, and dyes were obtained using the respective materials. Removal efficiency was compared, and removal efficiency was calculated using the following Equation 1.

[Calculation 1]

As a result, referring to FIG. 5 and Table 2, as a result of comparing the dye removal efficiency by CB [X] alone, the dye removal efficiency of CB [8] was the best, and the amine was better than CB [X] alone. It was confirmed that the dye removal efficiency of the DA-CB [X] complex having CB [X] bonded to the diatom modified with the group-containing silane compound was better. In addition, among the complexes, the DA-CB [8] complex showed the most excellent effect by improving dye removal efficiency by about 10-40 times compared to the conventional one.

type E (Abs / mg) CB [5] 0.046 CB [6] 0.055 CB [7] 0.062 CB [8] 0.071 DA-CB [5] 0.109 DA-CB [6] 0.115 DA-CB [7] 0.116 DA-CB [8] 0.119

4) Mixed Dye Removal Effect of Diatom-Cookerbituril8 Complex

To 1 ml of a mixed dye solution of rhodamine B and methylene blue, DA-CB [8] (50 mg / ml DA, 0.001 mg / ml CB [8]) complex was added and 5 hours Reaction was carried out to analyze the effect of mixed dye removal by DA-CB [8] complex.

As a result, referring to Figure 6, after the DA-CB [8] complex treatment, the absorbance was reduced with time, it was confirmed that the excellent dye removal efficiency improved about 10 times.

Example 3: Analysis of Dye Removal Efficiency Using Filter

1) Dye Removal Effect of Diatom-Cookerbituril8 Complex

Although the dye removal efficiency of the DA-CB [X] complex was found to be higher than that of CB [X] alone, there is a time constraint of about 1-4 hours for the DA-CB [X] complex to bind with the dye. Therefore, in order to overcome this, it was confirmed that the DA-CB [X] complex was applied to a tube equipped with a 0.45 μm membrane filter to solve the time problem.

Diatom alone (D) (50 mg / mL), Diatom (DA) modified with amine group-containing silane compound (50 mg / mL), Cucurbituril 8 (CB [8]) (0.001 mg / mL), Diatom-cookerbituril 8 (D-CB [8]) (50 mg / ml D, 0.001 mg / ml CB [8]), diatom-cookerbituril8 (DA-CB [8]) modified with amine group-containing silane compound (50 mg / ml DA, 0.001 mg / ml CB [8]) solutions were prepared respectively, and then each solution was added to 500 μL of trypan blue solution (Abs: 0.66) and transferred to a filter column. Thereafter, the absorbance of the filtered solution was measured by centrifugation for 20 seconds.

As a result, referring to FIG. 7, the DA-CB [8] complex required some time to bind to the dye and then the dye bound to the complex was removed. Could be removed to remove.

As described above in detail certain parts of the present invention, it is apparent to those skilled in the art that these specific descriptions are merely preferred embodiments, and the scope of the present invention is not limited thereto. Thus, the substantial scope of the present invention will be defined by the appended claims and equivalents thereof.

The scope of the present invention is represented by the following claims, and it should be construed that all changes or modifications derived from the meaning and scope of the claims and their equivalents are included in the scope of the present invention.

Claims (11)

Diatoms modified with silane compounds; And a cucurbituril, which is represented by Formula 1 below, and binds to an amine group of the silane compound;
[Formula 1]

In Formula 1 n is an integer of 5 to 8. The complex according to claim 1, wherein the silane compound is a compound represented by the following Chemical Formula 2:
[Formula 2]

Wherein R ¹ to R ³ may each be the same or different, either C1 to C4 alkyl or C1 to C4 alkoxy, R ⁴ is amino (C1 to C10) alkyl, 3- (2-amino ( C1 to C4) alkylamino) (C1 to C4) alkyl or 3- [2- (2-amino (C1 to C4) alkylamino) (C1 to C4) alkylamino] (C1 to C4) alkyl. The method of claim 2, wherein the silane compound is (3-aminopropyl) triethoxysilane (APTES), (3-aminopropyl) trimethoxysilane ((3-aminopropyl) trimethoxysilane), (1-aminomethyl) triethoxysilane ((1-aminomethyl) triethoxysilane), (2-aminoethyl) triethoxysilane, (4-aminobutyl) triethoxysilane (( 4-aminobutyl) triethoxysilane), (5-aminopentyl) triethoxysilane, (6-aminohexyl) triethoxysilane, 3-aminopropyl ( 3-aminopropyl (diethoxy) methylsilane, N- [3- (trimethoxysilyl) propyl] ethylenediamine, N- [3- (trimethoxysilyl) propyl] ethylenediamine, [3- (2- Aminoethylamino) propyl] trimethoxysilane ([3- (2-aminoethylamino) propyl] trimethoxysilane; AEAPTMS) and 3-[(trimethoxysilyl) propyl] diethylenetriamine (3 [(trimethoxysilyl) propyl] diethylenetriamine ; TM PTA) any one selected from the group consisting of complex. The complex of claim 1, wherein the amine group of the silane compound is noncovalently bonded to cucurbituril. Desalination or water purification composition comprising the complex of any one of claims 1 to 4. Desalination or water purification membrane filter comprising the complex of any one of claims 1 to 4. The membrane filter of claim 6, wherein the membrane filter is selected from the group consisting of a reverse osmosis filter, a hollow fiber membrane filter, an ultrafiltration membrane filter, a nano- and micro-filtration membrane filter. Desalination or water purification treatment apparatus comprising a complex of any one of claims 1 to 4. The wastewater purification treatment method comprising the step of removing the pollutants by treating the complex of any one of claims 1 to 4. 10. The method of claim 9, wherein the pollutant is selected from the group consisting of organic dyes, heavy metals, and radioisotopes. The desalination treatment method comprising the step of treating the complex of any one of claims 1 to 4 in a solution containing salt.

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