KR101818481B1 - Floating film for removing green tide, and floating film for purification of wastewater - Google Patents
Floating film for removing green tide, and floating film for purification of wastewater Download PDFInfo
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- KR101818481B1 KR101818481B1 KR1020150148267A KR20150148267A KR101818481B1 KR 101818481 B1 KR101818481 B1 KR 101818481B1 KR 1020150148267 A KR1020150148267 A KR 1020150148267A KR 20150148267 A KR20150148267 A KR 20150148267A KR 101818481 B1 KR101818481 B1 KR 101818481B1
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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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/002—Catalysts characterised by their physical properties
- B01J35/004—Photocatalysts
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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
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
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- E—FIXED CONSTRUCTIONS
- E02—HYDRAULIC ENGINEERING; FOUNDATIONS; SOIL SHIFTING
- E02B—HYDRAULIC ENGINEERING
- E02B15/00—Cleaning or keeping clear the surface of open water; Apparatus therefor
- E02B15/04—Devices for cleaning or keeping clear the surface of open water from oil or like floating materials by separating or removing these materials
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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
- C02F2303/00—Specific treatment goals
- C02F2303/16—Regeneration of sorbents, filters
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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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
A floating film for removing green algae, and a floating film for wastewater purification.
Description
The present invention relates to a floating film for removing green tide and a floating film for purifying wastewater.
Green algae occur in the Bukhang, Nakdong, and Geumgang in South Korea, which is a phenomenon in which eutrophic lakes and slow-flowing rivers grow in large quantities. Cyanobacteria such as microcystis, anaabena, Not only is it not good for cosmetics because it changes the color of the water significantly, it also has the seriousness to decay toxins, reduce the amount of dissolved oxygen, and disturb the water ecosystem. Most of the eutrophication and algal removal technologies in Korea have been dependent on the treatment of pollutants, that is, the reduction of pollutants concentration in the effluent water through wastewater treatment. Recently, the importance of the treatment of nonpoint pollutants among the causes of eco- Natural purification techniques have been studied and applied, but the level is still a basic stage. The technology for improving the efficiency of the green algae control technology through the control of the algae growth can be broadly divided into physical technology, chemical technology, and biological technology according to the characteristics. Some of the algae removal methods developed so far are as follows.
(1) Horticultural Spreading Method: By spraying loess, the vacant space between the loess particles absorbs and decomposes impurities and contaminants, thereby enriching the oxygen, and the colloid particles of the loess are suspended in the water (nutrients, micro-plankton, etc.) Aggregation, and adsorption. However, there is a problem that the loess spraying is one-time spraying, but it requires a lot of manpower and expense.
(2) Algae removal using sodium hypochlorite (NaOCl): A method of removing red tide by sodium hypochlorite produced by electrolysis of seawater. Since sodium hypochlorite has a bactericidal action, it destroys microorganisms causing red tide. After that, sodium hypochlorite returns to natural waters by natural light. However, since the above-described removal technique requires the use of seawater, it has disadvantages that it is used only for the removal of red sea.
(3) Sea surface recovery and sedimentation method: A pressurized floating separation device composed of centrifugal separator, coagulation preservation, mixing tank, and pressurized float tank is installed on the ship using an enemy hits treatment line. It was carried out in 1973-1974 as a consignment business of Japan National Fisheries Administration, but it was not able to obtain good effect and there was a problem in commercialization.
(4) Chemical Spraying Method: This method was mainly used in the United States to solve the occurrence of algae by using chemicals such as copper sulphate or organic compounds, which have a lethal power against algae from the past. However, these chemicals are known to affect other organisms, and their use on a large scale is neither sustainable nor economical.
(5) Ultrasonic treatment method: Ultrasonic waves were used to destroy the cells of algae. In addition, although it has been commercialized in Korea, it has been difficult to treat large-scale green tide and red tide due to the limitation of the range of generation of ultrasonic waves.
(6) Ozone treatment method: The ozone treatment method was an experiment conducted in the United States in 1977, and it was a method of recovering ozone by passing the ozone through an air pipe to promote the proliferation of red tide organisms. However, there is a disadvantage that it is expensive to generate ozone, and sterilizes not only algae but also other microorganisms.
(7) Elimination of algae by centrifugation: Separating, refining, and concentrating substances with different components or specific gravity by the action of centrifugal force, separating the crude substances in the liquid, and can be used continuously for a long time without replacing filters or parts. However, throughput is still as low as about 200 liters per hour, which is not economical.
(8) Algae removal using chemical coagulant (alum): It is a method of removing phosphorus and suspended matter along with algae by adding calcium, iron, aluminum, or its chemical coagulant with phosphorus removal ability to water. However, it is difficult to remove algae from the above coagulant in a lake dominated by paper which is resistant to coagulation sedimentation. In shallow lakes, there is also the side effect that sedimented aluminum, suspended matter and algae cells can be re-suspended by wind.
(9) Removal of reservoir algae using coherent flotation device: After the pollutants deposited by the high-pressure water injection device are taken up, various pollutants in the water are reacted with the chemicals to form aggregates, And then removed using a surface suction device or a scrape (a device for removing contaminants).
(10) Removal of green algae using fish: A method for reducing the hydration phenomenon by algae using phytoplankton-like fishes, which is a method for reducing the hydration phenomenon in the form of fish species (Paeoniae), a Korean endemic species, Fish, and fishes. Studies conducted in Europe have observed significant water quality improvements in appeal studies.
(11) Elimination of algae by plasma: A streamer discharge is used to remove algae in water by creating a streamer discharge with a gap of about 2 cm between electrodes using a stainless steel needle . However, in the above method, plasma is generated through high voltage pulse discharge in water and a lot of electricity is consumed.
However, since the conventional physical tide control method as described above has a problem of high cost, low practicality of the biological control method, and secondary pollution by the chemical treatment method, there is no certainty of a green tide removal method which is eco-friendly yet economical and effective . In order to prevent secondary pollution problems caused by long-term accumulation of loess or chemicals, it may be an eco-friendly and effective solution to produce a recoverable green algae film.
Graphene refers to a carbon atom monolayer in which a carbon atom with a sp 2 orbital is linked by a hexagonal ring structure. Graphene has attracted a great deal of attention from researchers over the past decades due to the very specific physicochemical properties of two-dimensional carbon nanosheets. Graphene has excellent electron conductivity, high thermal conductivity and permeability, which can be very useful as a basic material for the development of new materials. Further, since graphene is a two-dimensional nanosheet having excellent flexibility and strong tensile strength, a sample can be produced in the form of a film without a substrate (Korean Patent Laid-Open No. 10-2011-0073296). Although the antibacterial properties of graphene against E. coli are known, algae are more resistant to oxidation than E. coli, and it is difficult for graphene to destroy green algae.
Titanium oxide is a photocatalyst material having excellent light absorption ability and high light stability and excellent electron and hole mobility. In addition, the amount of titanium and oxygen which are constituent components is large, which is inexpensive, and durability and abrasion resistance are excellent, which is advantageous from the economical point of view. Particularly, the titanium oxide nanosheet having a layered structure is a two-dimensional nanosheet having strong tensile strength as in the case of graphene during peeling, so it is possible to prepare a sample in the form of a film without a substrate and to produce a hybrid film (Korean Patent Publication No. 10-1426269).
The present invention provides a floating film for removing green algae and a floating film for purifying wastewater.
However, the problems to be solved by the present invention are not limited to the above-mentioned problems, and other problems not mentioned can be clearly understood by those skilled in the art from the following description.
A first aspect of the present invention relates to a graphene film; Or a hybride film in which a metal oxide nanosheet or a metal hydroxide nanosheet is hybridized to a graphene film.
The second aspect of the present invention relates to a graphene film; Or a hybride film in which a metal oxide nanosheet or a metal hydroxide nanosheet is hybridized to a graphene film.
According to one embodiment of the present invention, a floating film can be produced by hybridizing a metal oxide nanosheet or a metal hydroxide nanosheet to a graphene film. The floating film having the ability to remove green algae according to one embodiment of the present invention is made of water It is not soluble or dispersed and has a floating property so that it can be recovered in its entirety so that it does not have a limit on the mass of the material to be removed, and it is environmentally friendly and economical because it can prevent secondary pollution.
According to one embodiment of the present invention, since the photocatalytic activity of the metal oxide nanosheets or the metal hydroxide nanosheets due to the mixing of the metal oxide nanosheets or the metal hydroxide nanosheets into the graphene film, The adsorption properties between the algae removing film and the algae eliminating film are controlled depending on the surface structure of the metal oxide nanosheets or metal hydroxide nanosheets and the uniform distribution of graphene and metal oxide nanosheets or metal hydroxide nanosheets, By maximizing the activity, it is possible to optimize the algae removing performance of the above-mentioned algae-removing film for removing green tea.
According to one embodiment of the present invention, a suspension film can be produced by hybridizing a metal oxide nanosheet or a metal hydroxide nanosheet to a graphene film, and the suspension film having a wastewater purification function according to an embodiment of the present invention can be produced by mixing water It is not dissolved or dispersed and has a floating property, so that the whole amount can be recovered.
According to one embodiment of the present invention, since the metal oxide nanosheets or the metal hydroxide nanosheets are mixed with the graphene film, the photocatalytic activity of the metal oxide nanosheets or the metal hydroxide nanosheets causes the wastewater purification The performance of the metal oxide nanosheets or metal hydroxide nanosheets or the metal hydroxide nanoparticles is controlled according to the surface structure of the metal oxide nanosheets or the metal hydroxide nanosheets, The uniform distribution of the nanosheets maximizes the photocatalytic activity and thus the wastewater purification performance of the floating film for wastewater purification can be optimized.
Figures 1 (a) and 1 (b) show structural models of the lepidocrocite-structured titanium oxide nanosheet (a) and the trititanate-structured titanium oxide nanosheet (b) in one embodiment of the invention .
2A and 2B are schematic cross-sectional views illustrating a method for producing a graft film (a), a graphene-redeposited titanium oxide hybrid film (b), and a graphene-trititanate structure titanium oxide Photograph of the hybrid film (c) and photograph of the floating test.
FIGS. 3 (a) to 3 (c) are graphs showing the relationship between the graphene film (a), the graphene-redeposited titanium oxide hybrid film (b) and the graphene- X-ray diffraction analysis graph of the structure titanium oxide hybrid film (c).
FIGS. 4 (a) to 4 (c) are cross-sectional views illustrating a method of manufacturing a semiconductor device according to an embodiment of the present invention, wherein the graphene film (a), the graphene- 2 is a scanning electron microscope (SEM) photograph of the structure titanium oxide hybrid film (c).
FIG. 5A is a graph showing the results obtained by using the graphene-redeposited titanium oxide hybrid film (a), the graphene-trititanate structure titanium oxide hybrid film (b), the graphene film (c) And control group (d).
FIG. 5B is a graph showing a greening removal experiment graph of a graphene-reddissociation structure titanium oxide hybrid film, a graphene-trititanate structure titanium oxide hybrid film, a graphene film, and a control group in one embodiment of the present invention.
6 (a) to 6 (c) are cross-sectional views illustrating a method for producing a graphene-redeposited titanium oxide hybrid film (a), a graphene-trititanate structure titanium oxide hybrid film (b) , And graphene film (c) after the experiment of removing green algae.
FIG. 7 is a graph showing the relationship between the graphene-reedocrocite structure titanium oxide hybrid film (a), the graphene-trititanate structure titanium oxide hybrid film (b), and the control group (c) This is the result of purification experiment.
Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art can easily carry out the present invention. It should be understood, however, that the present invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. In the drawings, the same reference numbers are used throughout the specification to refer to the same or like parts.
Throughout this specification, when a part is referred to as being "connected" to another part, it is not limited to a case where it is "directly connected" but also includes the case where it is "electrically connected" do.
Throughout this specification, when a member is "on " another member, it includes not only when the member is in contact with the other member, but also when there is another member between the two members.
Throughout this specification, when an element is referred to as "including " an element, it is understood that the element may include other elements as well, without departing from the other elements unless specifically stated otherwise. The terms "about "," substantially ", etc. used to the extent that they are used throughout the specification are intended to be taken to mean the approximation of the manufacturing and material tolerances inherent in the stated sense, Accurate or absolute numbers are used to help prevent unauthorized exploitation by unauthorized intruders of the referenced disclosure. The word " step (or step) "or" step "used to the extent that it is used throughout the specification does not mean" step for.
Throughout this specification, the term "combination (s) thereof " included in the expression of the machine form means a mixture or combination of one or more elements selected from the group consisting of the constituents described in the expression of the form of a marker, Quot; means at least one selected from the group consisting of the above-mentioned elements.
Throughout this specification, the description of "A and / or B" means "A or B, or A and B".
Throughout this specification, the term "graphene " means that a plurality of carbon atoms are covalently linked to one another to form a polycyclic aromatic molecule, wherein the carbon atoms linked by the covalent bond are the same as the basic repeating
Throughout the specification, the term "graphene oxide" is also referred to as graphene oxide and may be abbreviated as "GO ". But it may include, but is not limited to, a structure in which a functional group containing oxygen such as a carboxyl group, a hydroxyl group, or an epoxy group is bonded on a single layer graphene.
Throughout this specification, the term "reduced graphene oxide" or "reduced graphene oxide" refers to a graphene oxide that has undergone a reduction process to reduce its oxygen content and can be abbreviated as "rGO" However, the present invention is not limited thereto.
Hereinafter, embodiments of the present invention are described in detail, but the present invention is not limited thereto.
A first aspect of the present invention relates to a graphene film; Or a hybrid film in which a metal oxide nanosheet or a metal hydroxide nanosheet is hybridized.
In one embodiment of the present invention, the green tide is a phenomenon in which a large amount of floating algae is proliferated in an eutrophic lake or a stream having a slow flow rate, and the alga is a microcystis, anabena, And may include, but is not limited to, microcystis.
In one embodiment of the present invention, the suspension film may be produced by hybridizing the metal oxide nanosheet or the metal hydroxide nanosheet with the graphene film, but the present invention is not limited thereto.
In one embodiment of the present invention, the floating film for removing green algae may decompose green tea by photocatalytic activity, but the present invention is not limited thereto.
In one embodiment of the present invention, the photocatalytic activity is exhibited by the introduction of the metal oxide nanosheets or the metal hydroxide nanosheets, thereby improving the algal removal performance of the floating film for removing green algae. However, . For example, the metal oxide nanosheet or the metal hydroxide nanosheet may be a titanium oxide nanosheet, specifically, a repidocrocite structure titanium oxide nanosheet or a trititanate structure titanium oxide. .
In one embodiment of the invention, the photocatalytic activity may be, but not limited to, visible in the visible and / or ultraviolet region.
In one embodiment of the present invention, the photocatalytic activity is exhibited by the introduction of the metal oxide nanosheets or the metal hydroxide nanosheets, thereby improving the algae removal performance of the graphene film for removing green tea, and the metal oxide nanosheets or the metal The adsorption property between the algae removing film and the algae is controlled according to the surface structure of the hydroxide nanosheets and the photocatalytic activity is maximized due to the uniform distribution of the graphene film and the metal oxide nanosheets or the metal hydroxide nanosheets, The weathering performance of the floating film may be optimized, but may not be limited thereto. For example, the metal oxide nanosheet or the metal hydroxide nanosheet may be a titanium oxide nanosheet, and may be, but is not limited to, a repidocrocite-structured titanium oxide nanosheet.
In one embodiment of the present invention, the green tin-removing performance according to the metal oxide nanosheets or the metal hydroxide nanosheets can be explained by FIGS. 1 (a) and 1 (b). FIG. 1 shows a structural model of a lepidocrocite-structured titanium oxide nanosheet (a) and a trititanate-structured titanium oxide nanosheet (b). The lepidocrocite structure is a structure in which titanium and oxygen are only corner- Flat structure, and the trititanate structure has an obliquely staggered structure in which titanium and oxygen share edge sharing and vertex sharing. Since the algae elimination reaction takes place between the algae and the algae removing substance, the surface properties of the algae removing substance can be controlled by controlling the crystal structure of the titanium oxides. For example, when the metal oxide nanosheet or the metal hydroxide nanosheet is a lepidocrocite-structured titanium oxide nanosheet, a sharp nano-blade structure may be formed on the surface of the formed milky water releasing film. However, But may not be limited. For example, a sharp nano blade structure may be formed on the surface of the floating film due to the difference in shape and size between the graphene film and the nano-sheet of the refractory crocite structure. In addition, Thereby maximizing the removal of the green algae occurring between the algal removing material and the green algae. However, the present invention is not limited thereto.
In one embodiment of the present invention, the metal oxide nanosheet or the metal hydroxide nanosheet may be hybridized with the graphene film to form a layered structure, but the present invention is not limited thereto. For example, when the metal oxide nanosheet is a lepidocrocite-structured titanium oxide nanosheet, the nanotube is uniformly distributed on the graphene film to maximize the photocatalytic activity of the floating film for removing green algae But may not be limited thereto.
In one embodiment of the present invention, as the photocatalytic activity of the floating film for removing green alga can be maximized, the growth of the green algae formed may be suppressed, but the present invention is not limited thereto.
In one embodiment of the present invention, the graphene film may have a function of removing green algae by oxidizing power (oxidation reaction independent of active oxygen) through oxygen functional groups on the surface, but may not be limited thereto. For example, in general, a greenhouse can be removed according to the mechanism of oxidization and killing, that is, the photocatalytic principle, when the active oxygen is encountered. However, since the graphene film does not generate active oxygen, the green tide may be removed by oxidizing and killing the green tide by a small amount of oxygen functional groups on the surface of the graphene film, but the present invention is not limited thereto.
In one embodiment, the metal oxide nanosheets or metal hydroxide nanosheets may be formed of one or more of aluminum (Al), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn) (Co), Ni, Cu, Zn, Ga, Y, Zr, Mo, Nb, Sn, (Ru), Rh, Rh, Pd, Ag, Cd, Sb, In, tantalum, tungsten, rhenium, An oxide of a metal selected from the group consisting of platinum (Pt), gold (Au), lead (Pb), bismuth (Bi), and combinations thereof or a hydroxide of a metal. For example, the metal oxide nanosheet or the metal hydroxide nanosheet may be a titanium oxide nanosheet. Specifically, the metal oxide nanosheet may include a redox crystal structure titanium oxide nanosheet or a trititanate structure titanium oxide. However, But may not be limited thereto.
In one embodiment of the present invention, the algae-removing film for removing green alga can be recovered after use for removing green algae, but may not be limited thereto. For example, the floating film for removing green tea is not dissolved or dispersed in water, and may have a floating property. Therefore, the greenhouse can be recovered after adsorption and / or removal, and may be reused.
In one embodiment of the present invention, the floating property of the floating film for removing green alga can be water, alcohol, or an organic solvent, but the present invention is not limited thereto. For example, the alcohol may include, but is not limited to, ethanol, methanol, propanol, or butanol. For example, the organic solvent may include, but is not limited to, hexane, chloroform, acetone, benzene, carbon tetrachloride, or dimethylsulfoxide.
In one embodiment of the invention, the graphene film may comprise, but is not limited to, selected from the group consisting of graphene, graphene oxide, reduced graphene oxide, and combinations thereof.
In one embodiment of the present invention, the thickness of the floating film for removing green alga can be about 100 μm or less, but the present invention is not limited thereto. For example, the thickness of the buffalo film for removing green tea is about 100 mu m or less, about 1 mu m to about 100 mu m, about 5 mu m to about 100 mu m, about 10 mu m to about 100 mu m, about 20 mu m to about 100 mu m From about 30 microns to about 100 microns, from about 40 microns to about 100 microns, from about 50 microns to about 100 microns, from about 60 microns to about 100 microns, from about 70 microns to about 100 microns, from about 80 microns to about 100 microns, From about 1 micron to about 50 microns, from about 1 micron to about 50 microns, from about 1 micron to about 100 microns, from about 1 micron to about 90 microns, from about 1 micron to about 80 microns, from about 1 micron to about 70 microns, To about 40 microns, from about 1 microns to about 30 microns, from about 1 microns to about 20 microns, or from about 1 microns to about 10 microns.
In one embodiment of the present invention, by using the floating film for removing green algae, the algae phenomenon can be suppressed by about 24% or more as compared with the control without using the floating film for removing green tea, have.
The second aspect of the present invention relates to a graphene film; Or a hybride film in which a metal oxide nanosheet or a metal hydroxide nanosheet is hybridized to a graphene film.
In one embodiment of the present invention, a suspension film having a wastewater purification function may be produced by hybridizing the metal oxide nanosheet or the metal hydroxide nanosheet to the graphene film, but the present invention is not limited thereto.
In one embodiment of the present invention, the floating film for wastewater purification may have a photocatalytic activity for decomposing pollutants in the wastewater, but may not be limited thereto.
In one embodiment of the present invention, photocatalytic activity is exhibited by the introduction of the metal oxide nanosheets or the metal hydroxide nanosheets, thereby improving the wastewater purification performance of the wastewater treatment flocculant film. However, the present invention is not limited thereto have. For example, the metal oxide nanosheet or the metal hydroxide nanosheet may be a titanium oxide nanosheet, specifically, a repidocrocite structure titanium oxide nanosheet or a trititanate structure titanium oxide. .
In one embodiment of the invention, the photocatalytic activity may be, but not limited to, visible in the visible and / or ultraviolet region.
In one embodiment of the present invention, the photocatalytic activity is exhibited by the introduction of the metal oxide nanosheets or the metal hydroxide nanosheets, thereby improving the wastewater purification performance of the graphene film for purifying wastewater, and the metal oxide nanosheets or the metal The adsorption property between the floating film for purification of wastewater and contaminants in the wastewater is controlled according to the surface structure of the hydroxide nanosheet and the uniform distribution of the graphene film and the metal oxide nanosheets or the metal hydroxide nanosheets, By maximizing the activity, the waste water purification performance of the floating film can be optimized, but it may not be limited thereto. For example, the metal oxide nanosheet or metal hydroxide nanosheet may be a titanium oxide nanosheet, and may be, but is not limited to, a redox crystal structure titanium oxide nanosheet.
In one embodiment of the present invention, since the wastewater purification reaction occurs between a contaminant in the wastewater and a substance that removes the contaminant, controlling the crystal structure of the titanium oxide controls the surface property of the contaminant- For example, when the metal oxide nanosheet or the metal hydroxide nanosheet is a lepidocrocite-structured titanium oxide nanosheet, a sharp nano blade structure may be formed on the surface of the formed floating water-repellent film for wastewater purification , But may not be limited thereto. For example, a sharp nano blade structure may be formed on the surface of the floating film due to the difference in shape and size between the graphene film and the nano-sheet of the reversed-crocite structure, The adsorption of the material may maximize the purification of the wastewater, but may not be limited thereto.
In one embodiment of the present invention, the metal oxide nanosheet or the metal hydroxide nanosheet may be hybridized with the graphene film to form a layered structure, but the present invention is not limited thereto. For example, when the metal oxide nanosheet is a lepidocrocite-structured titanium oxide nanosheet, the photocatalytic activity of the floating film for purification of wastewater formed by uniformly distributing the nanosheet on the graphene film may be maximized However, the present invention is not limited thereto.
In one embodiment of the present invention, as the photocatalytic activity of the floating film for wastewater treatment is maximized, the growth of contaminants formed in the wastewater can be suppressed, but the present invention is not limited thereto.
In one embodiment of the present invention, the graphene film may have a wastewater purification function by oxidation reaction independent of active oxygen, but may not be limited thereto. For example, in general, contaminants in wastewater can be removed according to a mechanism that is oxidized and decomposed when the active oxygen is encountered, that is, the photocatalytic principle. However, since the graphene film does not generate active oxygen, contaminants in the wastewater can be removed by oxidizing and decomposing contaminants in the wastewater by a small amount of oxygen functional groups present on the surface of the graphene film. However, have.
In one embodiment, the metal oxide nanosheets or metal hydroxide nanosheets may be formed of one or more of aluminum (Al), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn) (Co), Ni, Cu, Zn, Ga, Y, Zr, Mo, Nb, Sn, (Ru), Rh, Rh, Pd, Ag, Cd, Sb, In, tantalum, tungsten, rhenium, An oxide of a metal selected from the group consisting of platinum (Pt), gold (Au), lead (Pb), bismuth (Bi), and combinations thereof or a hydroxide of a metal. For example, the metal oxide nanosheets or metal hydroxide nanosheets may be titanium oxide nanosheets. Specifically, the metal oxide nanosheets or the metal hydroxide nanosheets may include a redox crystal structure titanium oxide nanosheet or a trititanate structure titanium oxide. But may not be limited.
In one embodiment of the present invention, the floating film for purification of wastewater may be recoverable after use for wastewater purification, but may not be limited thereto. For example, the floating film for purification of wastewater may not be dissolved or dispersed in water, but may have a floating property, and may be recovered after adsorbing and / or removing contaminants in the wastewater and reused. However, the present invention is not limited thereto.
In one embodiment of the present invention, the floating property of the floating film for wastewater purification may be water, alcohol, or an organic solvent, but the present invention is not limited thereto. For example, the alcohol may include, but is not limited to, ethanol, methanol, propanol, or butanol. For example, the organic solvent may include, but is not limited to, hexane, chloroform, acetone, benzene, carbon tetrachloride, or dimethylsulfoxide.
In one embodiment of the invention, the graphene film may comprise, but is not limited to, selected from the group consisting of graphene, graphene oxide, reduced graphene oxide, and combinations thereof.
In one embodiment of the present invention, the thickness of the floating film for wastewater purification may be about 100 mu m or less, but the present invention is not limited thereto. For example, the thickness of the buffer film for wastewater purification may be about 100 탆 or less, about 1 탆 to about 100 탆, about 5 탆 to about 100 탆, about 10 탆 to about 100 탆, about 20 탆 to about 100 탆, From about 30 microns to about 100 microns, from about 40 microns to about 100 microns, from about 50 microns to about 100 microns, from about 60 microns to about 100 microns, from about 70 microns to about 100 microns, from about 80 microns to about 100 microns, from about 90 microns From about 1 micron to about 50 microns, from about 1 micron to about 50 microns, from about 1 micron to about 100 microns, from about 1 micron to about 90 microns, from about 1 micron to about 80 microns, from about 1 micron to about 70 microns, But may not be limited to, about 40 microns, about 1 microns to about 30 microns, about 1 microns to about 20 microns, or about 1 microns to about 10 microns.
Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited thereto.
[ Example ]
Grapina Production of film colloids
Graphite was oxidized by a modified Hummers' method to prepare graphite oxide. The synthesized graphite oxide was added to distilled water of 0.5 wt% and ultrasonic wave was applied to obtain exfoliated graphene oxide colloid. 0.175 wt% of hydrazine was added to the obtained graphene oxide colloid together with ammonia at 80 ° C for 1 hour to obtain a reclaimed graphene film colloid.
Preparation of titanium oxide colloid
TiO 2 and CsCO 3 / Na 2 CO 3 were mixed in an equivalent amount and solid-phase synthesis was performed at 800 ° C. for 24 hours to obtain Cs 0.67 Ti 1.83 □ 0.17 O 4 / Na 2 Ti 3 O 7 (□ denotes the defect of the atom, And can be omitted). To a 1 M HCl solution, add Cs 0 . 67 Ti 1 .83 □ put 0.17 O 4 / Na 2 Ti 3
Titanium oxide- Grapina hybrid Production of film
The prepared graphene film colloid and the prepared titanium oxide nanosheet colloid (Ti 1.83 O 4 or Ti 3 O 7 ) were mixed to prepare a mixed solution. The mixed solution was dialyzed with distilled water to remove TBA and hydrazine. The dialyzed solution was filtered under reduced pressure and dried at room temperature. After drying, the graphene-titanium oxide nanosheet hybrid film was removed from the anodisc.
(B) a graphene-redeposited titanium oxide hybrid film, (c) a graphene-trie structure, and (c) a graphene- (FIG. 2A) of a titanate-structured titanium oxide hybrid film, and a photograph (FIG. As shown in FIG. 2B, the graphene-titanium oxide hybrid film (graphene-reedocrocite-structured titanium oxide hybrid film or graphene-trititanate-structured titanium oxide hybrid film) as well as the graphene film has a floating property It is easy to apply as a material for removing green algae that can be recovered.
Analysis of floating film for removing green algae
In order to confirm the structures of the graphene film, the graphene-redeposited titanium oxide hybrid film and the graphene-trititanate-structured titanium oxide hybrid film produced in the above Examples, X Ray diffractometer (Rigaku, μ = 1.5418 Å, Ni-filtered Cu K α -radiation) and a scanning electron microscope (Jeol, JSM-6700F). As shown in Figs. 3 (a) to 3 (c), the X-ray diffraction pattern of the graphene film (Fig. 3 (a)) shows that graphene nanosheets are piled up in the (001) . In the case of the diffraction pattern of the graphene-lepidocrocite-structured titanium oxide hybrid film (FIG. 3 (b)), it can be seen that titanium oxide nanosheets are piled in the (001) It can be seen that the graphene is uniformly distributed among the lepidocrocite-structured titanium oxide nanosheets. On the other hand, the X-ray diffraction pattern of the graphene-triatitanate structure titanium oxide hybrid (Fig. 3 (c)) shows that the crystal plane of graphene is observed together with the crystal plane of the triatitanate structure titanium oxide, It can be seen that these titanium oxides are densely present in local portions of the titanate-structured titanium oxide.
4 (a) to 4 (c) are cross-sectional views of the graphene-redeposited titanium oxide hybrid film (b) and the graphene-trititanate structure titanium oxide hybrid film (c) It is a scanning electron microscope photograph. The pure graphene film has a smooth surface structure composed of a two-dimensional graphene plate. On the other hand, in the case of the reversed graphite-structured titanium oxide hybrid film, a sharp nano-blade structure is formed on the surface due to the difference in shape and size of the two nanosheets. It has been known from the prior reports that formation of such a surface structure plays an important role in antibacterial properties. Trititanate Structure The titanium oxide hybrid film shows a structure in which a titanium oxide sheet having a trititanate structure protruding from the surface of the belt is formed without a sharp surface structure. As can be seen from the X-ray diffraction pattern analysis in FIG. 3, in the case of the triatitanate-structured titanium oxide, graphene is concentrated in the local region of the titanium oxide, and the surface that appears only when the two nanosheets are well- Which means that the nano-blade structure is not formed effectively.
Green algae removal experiment
A graphene film, a graphene-lepidocrocite-structured titanium oxide hybrid film, and a graphene-trititanate-structured titanium oxide film were each floated in a microsyte algae solution having a concentration of 1.325 x 10 7 cells / mL. The floating films for removing green algae were placed in an incubator at 25.0 ° C equipped with a fluorescent lamp, irradiated with light of 2000 lux every 12 hours, and cultured in a greenhouse. As shown in Figs. 5A and 5B, after 7 days, the chlorophyll-a was extracted from the green tide to relatively quantify the degree of propagation of the green tide.
(A) a graphene-redeposited titanium oxide hybrid film, (b) a graphene-trititanate structure titanium oxide hybrid film, (c) a graphene film, and (d) A graph showing the removal of chlorophyll a from the algae solution photograph and the algae after 7 days of the algae removal experiment by floating the control in water and quantifying the algae removal activity. In the case of the control group in which no algae removing film was added, the green tide was proliferated and showed a dark green solution light. In contrast, in both types of graphene-titanium oxide hybrid films, green growth was inhibited and the color of the solution was lighter than that of the control. The graphene-redeposited titanium oxide hybrid film exhibited green growth inhibition activity of 24.4% for graphene film, 87.5% for graft-trititanate-structured titanium oxide hybrid film, and 93.7% for graphene-redeposited titanium oxide hybrid film. Considering the algae elimination performance of the graphene-titanium oxide nanosheet hybrid film, which is far superior to the graphene film, it is believed that the photocatalytic action of the titanium oxide nanosheet contributes to enhance the algae removal activity. Particularly, among the two types of hybrid films, the graphene-lepidocrocite-structured titanium oxide hybrid film exhibited the best algae removing activity, which was confirmed by X-ray diffraction pattern and scanning electron microscope image analysis of FIG. 3 and FIG. 4 As can be seen from the results, the uniform distribution of the graphene and titanium oxide nanosheets contributed greatly to maximizing the photocatalytic activity of the hybrid film.
6 (a) to 6 (c) are graphs showing the relationship between the graphene-reedocrocite structure titanium oxide hybrid film (a), the graphene-trititanate structure titanium oxide hybrid film (b) This is a scanning electron microscope (SEM) image of the algae adsorbed on the surface after the removal experiment. As shown in Figs. 6 (a) to 6 (c), it is observed that the greatest amount of algae is adsorbed on the surface of the graphene-redeposited titanium oxide hybrid film. This suggests that it is possible to optimize the algae removal performance by controlling the adsorption properties between the algae removing film and the algae depending on the structure of the titanium oxide nanosheets hybridized with the graphene.
Wastewater purification experiment
A graphite-lepidocrocite-structured titanium oxide hybrid film and a graphene-trititanate-structured titanium oxide hybrid film were respectively floated in a methylene blue solution having a concentration of 5 νM. Changes in the concentration of methylene blue were observed one hour after irradiation of the films with 1 Sun intensity (Newport, Xe lamp, solar simulator) with no control film.
7 (a) to 7 (c) show the graphene-redeposited titanium oxide hybrid film (a), the graphene-trititanate structure titanium oxide hybrid film (b) and the graphene- And (c) waste water purification test results of the control group. After 1 hour of solar irradiation, it was observed that the methylene blue solution concentration was lower in both the graphene-redeposited titanium oxide hybrid film and the graphene-trititanate-structured titanium oxide hybrid film compared to the control, Suggesting that the oil film is suitable for use as a recoverable waste water purification material.
It will be understood by those of ordinary skill in the art that the foregoing description of the embodiments is for illustrative purposes and that those skilled in the art can easily modify the invention without departing from the spirit or essential characteristics thereof. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive. For example, each component described as a single entity may be distributed and implemented, and components described as being distributed may also be implemented in a combined form.
The scope of the present invention is defined by the appended claims rather than the detailed description, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be construed as being included within the scope of the present invention.
Claims (14)
Wherein the graphene film comprises one selected from the group consisting of graphene, graphene oxide, reduced graphene oxide, and combinations thereof,
The titanium oxide nanosheet or the titanium hydroxide nanosheet has a lepidocrocite structure or a trititanate structure,
The floatability is for water, alcohol, or organic solvent,
The above-mentioned algae-releasing film for dissolving green algae is not dissolved or dispersed in water,
The algae-removing film for removing green algae is capable of recovering after use for removing green algae,
Wherein the thickness of the floating film for removing green tea is 100 mu m or less.
Floating film for algae removal.
Wherein the hybrid film is formed by hybridizing the titanium oxide nanosheet or the titanium hydroxide nanosheet to the graphene film to form a layered structure.
Wherein the hybrid film decomposes the green tide by photocatalytic activity.
Wherein the graphene film comprises one selected from the group consisting of graphene, graphene oxide, reduced graphene oxide, and combinations thereof,
The titanium oxide nanosheet or the titanium hydroxide nanosheet has a lepidocrocite structure or a trititanate structure,
The floatability is for water, alcohol, or organic solvent,
The floating film for purification of wastewater is not dissolved or dispersed in water,
The suspended film for purification of wastewater is recoverable after being used for removing green algae,
Wherein the thickness of the floating film for purification of wastewater is 100 mu m or less,
Floating film for waste water purification.
Wherein the hybrid film is formed by hybridizing the grafted film with the titanium oxide nanosheet or the titanium hydroxide nanosheet to form a layered structure.
Wherein the hybrid film has a photocatalytic activity for decomposing contaminants in wastewater.
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