KR20170029746A - Treatment method and apparatus of water pollutants by surface modification nanodiamonds - Google Patents
Treatment method and apparatus of water pollutants by surface modification nanodiamonds Download PDFInfo
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- KR20170029746A KR20170029746A KR1020150126709A KR20150126709A KR20170029746A KR 20170029746 A KR20170029746 A KR 20170029746A KR 1020150126709 A KR1020150126709 A KR 1020150126709A KR 20150126709 A KR20150126709 A KR 20150126709A KR 20170029746 A KR20170029746 A KR 20170029746A
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- nanodiamonds
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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
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
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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
- C02F2305/02—Specific form of oxidant
Abstract
Description
The present invention relates to a method and an apparatus for selectively treating and oxidizing in-water pollutants using surface-modified nanodiamonds, and more particularly, to a method and an apparatus for selectively removing and removing various kinds of water pollutants using surface modified nanodiamonds, The present invention relates to a method and an apparatus for selectively treating and oxidizing an underwater pollutant using a surface modified nanodiamond, which is a new advanced oxidation water treatment technique that can efficiently control the oxidation and control of pollutants in water by using an active oxidizing agent generated from a peroxide / per sulfate system.
Advanced Oxidation Technology (Advanced Oxidation Technology, AOT) is a hydroxyl radical (and OH) or the sulfate radical (SO 4 -) and the water that can produce quick break down a variety of organic contaminants in a non-selective active oxidizing agent having a strong oxidizing power, such as It is pollution treatment technology.
Such high-level oxidation techniques are mainly used for technologies utilizing chemical agents and catalysts, technologies utilizing photochemical methods, and technologies utilizing electrical energy. Conventional advanced oxidation techniques have many drawbacks such as limited application pH range, high cost, and large amount of sludge production, which makes it difficult to apply in the field. Therefore, there is a demand for an underwater pollutant control technique that can solve such a problem.
SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems of the prior art, and it is an object of the present invention to provide a method for selectively adsorbing and removing various kinds of water pollutants using surface modified nanodiamonds and an active oxidizing agent produced in a nanodiamond / persulfate system The present invention provides a method and apparatus for selectively treating and oxidizing underwater pollutants using surface-modified nano-diamonds, which is a new advanced oxidation water treatment technology that can efficiently control the oxidation and control of pollutants in water.
According to an aspect of the present invention,
A step (S1-1) of producing a surface-modified nanodiamond; The step of injecting the surface-modified nanodiamond (S1-2); A selective adsorption elimination reaction step (S1-3) of aquatic pollutants; A method (S1) for selectively adsorbing and removing water contaminants comprising a step (S1-4) of recovering and regenerating the surface-modified nanodiamonds, and
A step (S2-1) of preparing a surface-modified nanodiamond; The introduction of the surface-modified nanodiamond and the injection of persulfate (S2-2); A step S2-3 of oxidizing and removing the pollutants in water; (S2) of recovering and regenerating the surface-modified nano-diamonds (S2-4).
The method for preparing the surface-modified nanodiamonds according to the present invention may include one or more of the following embodiments. For example, the surface of the nanodiamond may correspond to a modification of at least one of organic or inorganic materials.
The material that can be used for the surface modification may be any one of metal elements (nitrogen, boron, fluorine, sulfur etc.) on the periodic table and nonmetal elements (iron, copper, nickel, cobalt, titanium, etc.) It can be doped on the surface of a nanodiamond.
The apparatus for treating pollutants in water using a selective adsorption elimination reaction of a pollutant in water according to the present invention comprises a pollutant storage tank capable of storing water containing pollutants in water and a pollutant storage tank for adsorbing pollutants by surface- And an addition tank in which the surface modified nanodiamond can be added to the adsorption reaction tank and a purified water tank for storing purified water through the adsorption reaction tank.
The apparatus for treating pollutants in water using the surface modified nanodiamond / persulfate system according to the present invention comprises a pollutant storage tank capable of storing water containing pollutants in water, And an addition tank in which the nanodiamond and persulfate can be added to the oxidation reaction tank, and a purification tank for storing water purified through the oxidation reaction tank.
According to the present invention, a method and apparatus for selectively treating and oxidizing an underwater pollutant using the nanodiamond according to the present invention includes selective adsorption removal of various kinds of water pollutants using surface-modified nanodiamonds and an active oxidant generated in a nanodiamond / persulfate system It is possible to efficiently and selectively remove the pollutants in the water.
And it can be applied in all pH range, and it can effectively reduce energy cost, amount of catalyst input and sludge generation.
In addition, since it can be recovered and reused, the water pollutant can be economically controlled.
1 is a TEM photograph of a nano diamond,
FIG. 2 and FIG. 3 are photographs showing a mechanism for removing water pollutants by the selective adsorption and oxidation control technique of the water pollutant using the surface modified nanodiamond,
4 is a block diagram showing the selective adsorption removal of water pollutants and the oxidation and removal of water pollutants.
The terms and words used in the present specification and claims should not be construed to be limited to ordinary or dictionary meanings, but the inventor may appropriately define the concept of the term to describe its invention in the best way Can be interpreted as a meaning and a concept consistent with the technical idea of the present invention.
It should be noted that the embodiments described in this specification and the configurations shown in the drawings are merely preferred embodiments of the present invention and do not represent all the technical ideas of the present invention, It is to be understood that equivalents and modifications are possible.
Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.
As shown in FIG. 1 to FIG. 4, a selective adsorption / removal method (S1) of an underwater contaminant is a step (S1-1) of preparing a surface-modified nanodiamond; The step of injecting the surface-modified nanodiamond (S1-2); A selective adsorption elimination reaction step (S1-3) of aquatic pollutants; And a step (S1-4) of recovering and regenerating the surface-modified nanodiamonds.
The method (S2) for oxidizing and removing the pollutants in the water comprises a step (S2-1) of preparing a surface-modified nanodiamond; The introduction of the surface-modified nanodiamond and the injection of persulfate (S2-2); A step S2-3 of oxidizing and removing the pollutants in water; And a step (S2-4) of recovering and regenerating the surface-modified nanodiamonds.
1. Surface modification of nanodiamonds
In the present invention, commercially available nanodiamonds were purchased and the surface of the nanodiamonds was modified under various synthesis conditions.
Surface modified nanodiamonds are pickled nanodiamonds, surface oxidized nanodiamonds, surface hydrogenated nanodiamonds, and surface graphitized nanodiamonds. The surface modification step of the nanodiamonds of the present invention is as follows.
- Pickled nanodiamonds (Nanodiamond (ND))
Commercially available nanodiamonds are treated with 1 M sulfuric acid (H 2 SO 4 ) and then washed several times in distilled water (DI water)
- Surface oxidized nanodiamonds (Oxidized NDs (Oxi-ND))
The acid-treated nanodiamonds were annealed at 430 ° C for 5 hours at atmospheric flow conditions and then gradually cooled
- Hydrogenated-NDs (H-ND)
The acid-treated nanodiamonds were annealed at 800 ° C for 2 hours under hydrogen gas flow conditions (150 mL min -1 ), then gradually cooled
Surface Graphitized Nd Diamond (Graphitized NDs (G-NDs))
The acid-treated nanodiamonds were annealed at 1200 ° C for 2 hours under an argon gas flow condition (150 mL min -1 ), then gradually cooled
2. Treatment of surface pollutants with surface modified nanodiamonds
Two configuration diagrams of the selective adsorption and oxidation control technology of the surface modified nanodiamond based water pollutants developed in the present invention are shown in FIGS. 3 and 4. FIG.
The composition of the selective adsorption elimination technique of aquatic pollutants can be divided into the production of surface-modified nanodiamonds, the introduction of surface-modified nanodiamonds, the selective removal of adsorption of water pollutants, and the recovery and regeneration of surface-modified nanodiamonds .
In addition, the composition of the oxidative removal technique of the underwater pollutants includes the preparation of the surface modified nanodiamond, the injection of the surface modified nanodiamond and the injection of the persulfate, the oxidation removal reaction of the pollutant in the water and the recovery and regeneration of the surface modified nanodiamond .
The structure of the water pollutant treatment system of the present invention does not require the acidification and neutralization facilities used in the existing high-level oxidation technology, so that if the water treatment process can be simplified, the water treatment cost can be ultimately reduced.
3. Experiment to remove pollutants in water
3.1 Selective adsorption removal of pollutants in water
3.1.1 Experimental conditions
In the present invention, various surface-modified nano-diamonds were prepared. Examples of the reagent used in the present invention include phenol, bisphenol A, aniline, benzoic acid, acetaminophen, ranitidine, sulfamethoxazole, And Carbamazepine.
The pH of the initial reaction solution was adjusted to pH 7 with phosphate buffer solution and the initial pH of the reaction solution was adjusted with acid (HClO 4 ) and base (NaOH). The control reaction time of the pollutants in water of the present invention was adjusted to 1 hour, and the removal efficiency was confirmed according to the reaction time.
3.1.2 Experimental results
The removal efficiency of various contaminants was observed by selecting nanodiamonds that were surface-modified in various shapes (Graph 1).
The nanodiamides selected in the present invention are selected from the group consisting of pickled nanodiamonds (ND), surface oxidized nanodiamonds (Oxi-ND), surface hydrogenated nanodiamonds (H-ND) and surface graphitized nanodiamonds (G- . Studies have shown that surface-graphitized nanodiamonds easily adsorb and remove most contaminants.
In particular, oxidized nanodiamonds and hydrogenated nanodiamonds showed high removal efficiency selectively for certain contaminants.
The high selective removal efficiency of the oxidized nanodiamondes acetaminophen and aniline showed that the hydrogenated nanodiamonds had a high selective removal efficiency for sulfamethicone. The high selectivity of these surface modified nanodiamond contaminants can be a great advantage in the selective removal, recovery and separation of contaminants.
[Graph 1]
Selective removal of water pollutants using various surface modified nanodiamonds
[Acetaminophen] 0 = [Sulfamethoxazole] 0 = [Carbamazepine] 0 = [Ranitidine] 0 = [Aniline] 0 = [Bisphenol A] 0 = [Phenol] 0 = [Benzoic acid] 0 = 0.01 mM; [Nanodiamond] 0 = [Oxidized nanodiamond] 0 = [Hydrogenated nanodiamond] 0 = [Graphited nanodiamond] 0 = 0.5 gL -1 ; 1 mM phosphate buffer at pH 0 7; Reaction time = 60 min
3.2 Oxidation of pollutants in water
3.2.1 Experimental conditions
In the present invention, various surface-modified nanodiamonds were prepared, and multi-wall carbon nanotubes (MWCNTs), single wall carbon nanotubes (SWCNTs), graphene oxides (Graphite, Graphite oxide, Graphene oxide, Reduced graphene oxide) and fullerene (C 60 ).
Examples of the reagent used in the present invention include peroxodisulfate (PDS), phenol, bisphenol A, aniline, benzoic acid, acetaminophen, ranitidine ), Sulfamethoxazole, and carbamazepine. The pH of the initial reaction solution was adjusted to pH 7 using 1 mM phosphate buffer and the initial pH of the reaction solution was adjusted with acid (HClO 4 ) and base (NaOH). The control reaction time of the water pollution control of the present invention was adjusted to 1 hour, and the removal efficiency was confirmed with time.
3.2.2 Experimental results
In the present invention, various carbon materials including surface graphitized nanodiamonds were selected and the decomposition efficiency of phenol was observed using an active oxidant produced by activating persulfate (Graph 2).
The carbon materials used in the present invention include surface graphitized nanodiamonds, multi-walled carbon nanotubes, single-walled carbon nanotubes, graphene oxides, and fullerenes.
Research has shown that surface graphitized nanodiamonds and carbon nanotubes activate peroxides to effectively decompose phenols.
On the other hand, other carbon materials selected for the present invention did not effectively oxidize phenol. In particular, surface graphitized nanodiamonds showed the best ability to oxidize and remove phenol.
[Graph 2]
Oxidation of phenol using surface graphitized nanodiamond / persulfate system
[Phenol] 0 = 0.01 mM; [Fullerene C 60 ] 0 = [Graphite] 0 = [Graphite oxide] 0 = [Graphene oxide] 0 = [MWCNT] 0 = [SWCNT] 0 = [Graphite nanodiamond] 0 = 0.1 gL -1 ; [Peroxydisulfate] 0 = 1 mM; 1 mM phosphate buffer at pH 0 7; Reaction time = 60 min
Claims (4)
The step of injecting the surface-modified nanodiamond (S1-2);
A selective adsorption elimination reaction step (S1-3) of aquatic pollutants;
(S1) comprising a step (S1) of recovering and regenerating a surface-modified nanodiamond, and a step (S1) of removing and regenerating the surface-modified nanodiamond Method and apparatus.
The introduction of the surface-modified nanodiamond and the injection of persulfate (S2-2);
A step S2-3 of oxidizing and removing the pollutants in water;
(S2) of recovering and regenerating surface-modified nano-diamonds, wherein the surface-modified nanodiamonds are recovered and regenerated (S2-4). And apparatus.
The step of preparing the surface-modified nanodiamonds according to the present invention may further include the step of modifying the surface of the nanodiamonds with at least one of organic and inorganic materials. And an oxidation treatment method and apparatus.
The material that can be used for the surface modification may be any one of metal elements (nitrogen, boron, fluorine, sulfur etc.) and nonmetal elements (iron, copper, nickel, cobalt, titanium, etc.) on the periodic table of the elements, A method and apparatus for selective and oxidative treatment of aquatic pollutants using surface modified nanodiamonds, characterized in that the surface of diamond can be doped.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108083416A (en) * | 2017-12-21 | 2018-05-29 | 南昌航空大学 | A kind of method that carbon material activation persulfate orientation is carbonylated and generates singlet oxygen |
| KR20190139025A (en) * | 2018-06-07 | 2019-12-17 | (주)이데아이엔에스 | Permeable reactive barrier and the method for removing pollutants by using the same |
| CN111847626A (en) * | 2020-07-27 | 2020-10-30 | 南昌航空大学 | Device for pretreating complex heavy metal in electroplating cleaning wastewater by catalytic oxidation method and using method thereof |
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2015
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108083416A (en) * | 2017-12-21 | 2018-05-29 | 南昌航空大学 | A kind of method that carbon material activation persulfate orientation is carbonylated and generates singlet oxygen |
| CN108083416B (en) * | 2017-12-21 | 2020-12-01 | 南昌航空大学 | Method for directionally generating singlet oxygen by activating persulfate through carbon carbonylation material |
| KR20190139025A (en) * | 2018-06-07 | 2019-12-17 | (주)이데아이엔에스 | Permeable reactive barrier and the method for removing pollutants by using the same |
| CN111847626A (en) * | 2020-07-27 | 2020-10-30 | 南昌航空大学 | Device for pretreating complex heavy metal in electroplating cleaning wastewater by catalytic oxidation method and using method thereof |
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