CN113582226A - Preparation method of optical nano material for treating black and odorous water body - Google Patents
Preparation method of optical nano material for treating black and odorous water body Download PDFInfo
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- CN113582226A CN113582226A CN202110907438.8A CN202110907438A CN113582226A CN 113582226 A CN113582226 A CN 113582226A CN 202110907438 A CN202110907438 A CN 202110907438A CN 113582226 A CN113582226 A CN 113582226A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 230000003287 optical effect Effects 0.000 title claims description 27
- 239000000243 solution Substances 0.000 claims abstract description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000003756 stirring Methods 0.000 claims abstract description 25
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002244 precipitate Substances 0.000 claims abstract description 18
- 239000002245 particle Substances 0.000 claims abstract description 15
- 239000011259 mixed solution Substances 0.000 claims abstract description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 229960000583 acetic acid Drugs 0.000 claims abstract description 9
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- 238000004140 cleaning Methods 0.000 claims abstract description 6
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000000137 annealing Methods 0.000 claims description 16
- 238000005245 sintering Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
- 230000009467 reduction Effects 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- 239000003344 environmental pollutant Substances 0.000 abstract description 9
- 231100000719 pollutant Toxicity 0.000 abstract description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 7
- 239000011574 phosphorus Substances 0.000 abstract description 7
- 238000000746 purification Methods 0.000 abstract description 6
- 241000195493 Cryptophyta Species 0.000 abstract description 4
- 238000009395 breeding Methods 0.000 abstract description 3
- 230000001488 breeding effect Effects 0.000 abstract description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 35
- 239000013078 crystal Substances 0.000 description 10
- 239000004408 titanium dioxide Substances 0.000 description 10
- 241000196324 Embryophyta Species 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- -1 polychlorinated biphenyl compounds Chemical class 0.000 description 7
- 239000011651 chromium Substances 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 239000010865 sewage Substances 0.000 description 5
- 238000007667 floating Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 239000013049 sediment Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 229910003077 Ti−O Inorganic materials 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002352 surface water Substances 0.000 description 3
- 244000105624 Arachis hypogaea Species 0.000 description 2
- 240000003826 Eichhornia crassipes Species 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- 229910011208 Ti—N Inorganic materials 0.000 description 2
- 208000034699 Vitreous floaters Diseases 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 235000020232 peanut Nutrition 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 241000237519 Bivalvia Species 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 241000237858 Gastropoda Species 0.000 description 1
- 244000207740 Lemna minor Species 0.000 description 1
- 235000006439 Lemna minor Nutrition 0.000 description 1
- 235000001855 Portulaca oleracea Nutrition 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 231100000403 acute toxicity Toxicity 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
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- 238000010276 construction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 238000000695 excitation spectrum Methods 0.000 description 1
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- 230000007674 genetic toxicity Effects 0.000 description 1
- 231100000025 genetic toxicology Toxicity 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 231100001240 inorganic pollutant Toxicity 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
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- 230000036284 oxygen consumption Effects 0.000 description 1
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- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B01J35/23—
-
- B01J35/39—
-
- B01J35/617—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- 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
- C02F2303/02—Odour removal or prevention of malodour
-
- 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
- C02F2305/08—Nanoparticles or nanotubes
-
- 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
-
- 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
The invention discloses a preparation method of a light nano material for treating black and odorous water, belonging to the technical field of black and odorous water treatment and comprising the following steps: adding tetrabutyl titanate into absolute ethyl alcohol, and stirring uniformly to obtain a solution A; dissolving ammonia water in absolute ethyl alcohol, sequentially dripping glacial acetic acid and deionized water, and uniformly stirring to obtain a solution B; dropwise adding the solution B into the solution A while stirring to obtain a mixed solution; carrying out heat treatment on the mixed solution, cooling, centrifuging, cleaning a precipitate and drying; the dried precipitate is sintered and then is annealed, and the light nano material can remove pollutants (suspended particles, dissolved phosphorus and the like) in water, promote the rapid purification of the pollutants (organic matters, nitrogen, phosphorus and the like), kill or control the breeding of blue algae and improve the transparency of water.
Description
Technical Field
The invention relates to the technical field of black and odorous water body treatment, in particular to a preparation method of a light nano material for treating black and odorous water body.
Background
At present, the urban surface water pollution is serious, the increase speed of the discharge amount of the waste water is high from the overall situation, and the total amount of the urban domestic sewage is continuously increased. Due to the low treatment rate of the domestic sewage (about 20-30 percent), most of the domestic sewage is directly or indirectly discharged into urban rivers without being treated, and a large amount of industrial wastewater is discharged, so that the oxygen consumption organic pollutants and the nitrogen and phosphorus content of the rivers remain high, the water body eutrophication is serious and is black and odorous, the aquatic plants such as blue algae, water hyacinth, water peanuts and the like are bred explosively, the water environment of the rivers is seriously polluted, and the water ecological degradation of the rivers is accelerated. The serious deterioration of the urban river channel environment not only affects the sustainable development of urban economy, but also seriously affects the health and life of people due to poor water quality and bad smell.
At present, a microorganism strengthening technology, a biological membrane technology and a plant purification technology are adopted to treat black and odorous water, but the method has the following main problems: (1) the water quality of rivers is still poor, and the landscape quality is not high: the problems of turbidity, high nitrogen and phosphorus content, low dissolved oxygen and transparency and the like of river water generally exist, the number of V-type and poor V-type river channels is still as high as about 90%, and the treated river channels have more black and odorous rebounding phenomena. The deterioration of river landscape and water quality during rainy days, particularly heavy rains, is a common and prominent problem. (2) Silting a large amount of polluted bottom sludge: although the sediment dredging is widely applied to small-scale river regulation as one of the leading measures for river regulation, the investigation result shows that the rapid accumulation of the sediment in the dredged river is still quite common, mainly due to the high sewage (sewage and garbage) receiving intensity and the serious shortage of river network hydrodynamic force. The content of organic matters, heavy metals, nitrogen, phosphorus and the like in the bottom mud on the surface layer of the black and odorous river channel is high, and the decomposition and the resuspension of the bottom mud not only can aggravate the pollution of the overlying river water, but also can consume a large amount of DO. The sediment and the river water have certain acute, subacute and genetic toxicity, persistent toxic pollutants are enriched in organisms to different degrees along a food chain, and the toxicity of the sediment is higher than that of the river water. The influence of the dredging process of the polluted bottom mud on the water quality and the landscape of the river water and the in-situ stabilization and restoration of the dredged bottom mud are problems which are urgently needed to be solved in the deepening treatment of the black and odorous riverway. (3) Degradation and even collapse of the river water ecosystem: the aquatic organism community of the urban black and odorous riverway is incomplete in structure and not complete in function, the species number, particularly large aquatic organisms, is poor, the individual is miniaturized, and most of the aquatic organism community is resistant to pollution; the biodiversity is lower, the community type is mainly single superior community, and relatively intensively distributes on the surface layer of the water body, the substrate habitat is severe, and the ecological community is not suitable for the growth and the propagation of benthonic animals such as snails, clams and the like. Except for a few small river channels (which are subjected to ecological restoration treatment in recent years), at present, submerged plants and large aquatic animals in almost all urban rivers are completely killed. The ecological chain of the black and odorous river is extremely degraded, and the output, transfer and purification of pollutants cannot be completed, so that the pollutants are seriously blocked and vicious circle is caused. (4) The self-cleaning ability of river water is poor, algal blooms burst: the river water flow speed is slow, the water power is insufficient, the self-purification capability is not strong, and particularly the self-purification capability of a water body of a closed small river channel (one end is disconnected or the whole channel is separated) is poor, so that a large amount of floating algae are bred, and algal blooms are fulminated seasonally and stink. The breeding of water hyacinth, water peanuts, duckweed, algal blooms and the like is a problem which needs to be faced and urgently solved for a long time in the deep treatment of urban rivers.
Therefore, in order to solve the above problems, it is necessary to provide a new method for treating a black and odorous water body.
Disclosure of Invention
The invention aims to provide a preparation method of a light nano material for treating black and odorous water, which improves the treatment capacity of the black and odorous water.
In order to achieve the purpose, the invention provides the following scheme:
the invention provides a preparation method of a light nano material for treating black and odorous water, which comprises the following steps:
(1) adding tetrabutyl titanate into absolute ethyl alcohol, and stirring uniformly to obtain a solution A;
(2) dissolving ammonia water in absolute ethyl alcohol, sequentially dripping glacial acetic acid and deionized water, and uniformly stirring to obtain a solution B;
(3) dropwise adding the solution B into the solution A while stirring to obtain a mixed solution;
(4) carrying out heat treatment on the mixed solution, cooling, centrifuging, cleaning a precipitate and drying;
(5) sintering the dried precipitate, and then carrying out annealing treatment.
Further, the step (1) is tetrabutyl titanate (Ti (OBu))4) The volume ratio of the ethanol to the absolute ethyl alcohol is (1-2): 5.
further, the concentration of the ammonia water in the step (2) is 2mol/L, and the volume ratio of the ammonia water, the absolute ethyl alcohol, the glacial acetic acid and the deionized water is (3-5): 20: 1: 5.
further, the heat treatment temperature in the step (4) is 150-.
Further, the sintering temperature in the step (5) is 450-700 ℃, and the sintering time is 2-3 h.
Further, the annealing temperature in the step (5) is 200-.
Due to TiO2The semiconductor has a wider forbidden band width of 3.2eV, a corresponding wavelength of 387nm and belongs to an ultraviolet region, ultraviolet light only accounts for 3% -4% of sunlight reaching the surface of the earth, and the most visible light part (energy accounts for about 45%) in the solar spectrum is not effectively utilized. In the present invention, the degree of crystallinity without annealing is very low and is substantially amorphous; the crystal is in a polycrystalline state after annealing treatment at the temperature of 200-400 ℃, and N mainly exists in the TiO in a substitutional form after the annealing treatment2Polycrystalline junctionIn the structure, a small amount of gap N may form a small amount of Ti-N bonds with Ti, and doped N may overflow into the chamber, and N in the chamber may be generated due to the stronger Ti-O bonds2It is difficult to replace O in Ti-O bonds, therefore, the optical nano material contains Ti-N bonds and Ti-O bonds at the same time, contains mixed crystals of anatase and rutile, and leads TiO to be hybridized by the 2p orbital of N and the 2p orbital of O2The forbidden band of (A) is reduced, and TiO is increased due to N replacement2Is optically active. Therefore, the invention provides a light nano material, and nitrogen replaces a small amount of lattice oxygen to enable TiO to be subjected to oxidation treatment2The band gap is narrowed, the ultraviolet light activity is not reduced, and the visible light activity is achieved, so that the treatment effect on the black and odorous water body is improved.
The invention also provides the optical nano material for treating the black and odorous water body, which is prepared by the preparation method, wherein the average particle size of the optical nano material is 20-40nm, and the addition amount of the optical nano material for treating the black and odorous water body is 0.03-0.05 g/L.
Under the irradiation of light, the light nano material is excited to generate an 'electron-hole' pair, the 'electron-hole' pair is a high-energy particle, and after the 'electron-hole' pair reacts with surrounding water and oxygen, a system with extremely strong oxidation-reduction capability is formed, and organic matters adsorbed on the surface of the 'electron-hole' pair can be rapidly degraded into CO2And H2And small molecules such as O and the like can degrade various organic pollutants including polycyclic aromatic hydrocarbons and polychlorinated biphenyl compounds which are difficult to degrade, and can reduce inorganic pollutants such as cyanogen, chromium and the like contained in the wastewater.
The titanium dioxide photocatalysis efficiency can generate superoxide and hydroxyl free radical under the irradiation of ultraviolet ray and visible light by generating reactive active oxygen and singlet oxygen. However, when the size of titanium dioxide ions is as small as a few nanometers, the photocatalytic activity is lost, because charges and cavities can not be formed on the surfaces of the particles, the average particle size is controlled to be 20-40nm through the adjustment of the preparation method to reduce the probability of titanium dioxide charge/cavity recombination, meanwhile, the surface structure of the optical nano material is rough, the adhesion force of pollutants can be increased, the pollutants can be better absorbed due to a short transportation path, the excitation spectrum of the titanium dioxide can be widened to the visible region range through doping, and the possibility of realizing the in-situ degradation of the pollutants in a complex environment is provided.
The invention discloses the following technical effects:
the prepared optical nano material has unique crystal structure and surface characteristics, the quantum size effect of the nano particles enables the energy gap of a semiconductor to be widened, the potential of a conduction band to be more negative, and the potential of a valence band to be more positive, so that the optical nano material has stronger oxidation-reduction capability. In addition, the particle size of the particles is small (the average particle size is 20-40nm), so that the probability of electron and hole recombination is smaller, charge separation is facilitated, the catalytic activity is improved, and the optical nano material has high activity and selectivity for catalytic oxidation, reduction and cracking reactions.
The light nano material can remove pollutants (suspended particles, dissolved phosphorus and the like) in water, promote the rapid purification of the pollutants (organic matters, nitrogen, phosphorus and the like), kill or control the breeding of blue algae and improve the transparency of the water body.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The description and examples are intended to be illustrative only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
Example 1
First, 8mL Ti (OBu)4Adding the mixture into 40mL of absolute ethyl alcohol, stirring and dissolving until the mixture is uniform to obtain a solution A; dissolving 5mL of 2mol/L ammonia water in 20mL of absolute ethyl alcohol, sequentially dripping 1mL of glacial acetic acid and 5mL of deionized water, and uniformly stirring to obtain a solution B (the pH value is 3-4); dropwise adding the solution B into the solution A, stirring while dropwise adding, stirring for 30min after dropwise adding to obtain a mixed solution, transferring the mixed solution into a 200mL polytetrafluoroethylene stainless steel reaction kettle, putting the reaction kettle into an oven, carrying out heat treatment at 150 ℃ for 10h, cooling, carrying out centrifugal separation on the liquid, washing precipitates for 3 times by using absolute ethyl alcohol and deionized water respectively, drying the precipitates for 4h at 100 ℃, sintering the precipitates for 3h at 450 ℃ in a box-type resistance furnace, annealing for 120min at 300 ℃ in a nitrogen atmosphere at the cooling rate of 30 ℃/min to obtain the nano-material. In this example, the average particle size of the optical nano material is about 38nm, and through detection, the titanium dioxide in the optical nano material has two crystal forms of anatase and rutile, and the specific surface area is 626m2The photoresponse range is 310-810 nm.
The light nano material prepared in the embodiment is used for treating black and odorous watercourses in certain places of Jilin, and the conditions before treatment are as follows: narrowing of river surface, silting of river bed, water falling, emergence of beach, weed clustering, poor self-cleaning ability of water body, and cut-off in most of time(ii) a The bridge and culvert construction standard in the water system is low, the water passing section is small, the culvert bottom is high, and the flowing water is not smooth. After cleaning up river channel garbage, weeds and river surface floating objects, adding the materials according to the addition of 0.05g/L, and after 2 months, the transparency of the water body is gradually improved and the odor disappears after the treatment, the pH value is stabilized between 7.0 and 7.5, the dissolved oxygen is about 4.1mg/L, the ammonia nitrogen is maintained below 2mg/L, and the COD isCrThe water quality of the water body is maintained below 30mg/L, and the water quality reaches III-class water quality standard of the surface water environment of the people's republic of China (GB 3838-.
Example 2
First, 16mL Ti (OBu)4Adding the mixture into 40mL of absolute ethyl alcohol, stirring and dissolving until the mixture is uniform to obtain a solution A; dissolving 4mL of 2mol/L ammonia water in 20mL of absolute ethyl alcohol, sequentially dripping 1mL of glacial acetic acid and 5mL of deionized water, and uniformly stirring to obtain a solution B (the pH value is 3-4); dropwise adding the solution B into the solution A, stirring while dropwise adding, stirring for 30min after dropwise adding to obtain a mixed solution, transferring the mixed solution into a 200mL polytetrafluoroethylene stainless steel reaction kettle, putting the reaction kettle into an oven, carrying out heat treatment at 180 ℃ for 8h, carrying out centrifugal separation on the liquid after cooling, washing precipitates for 3 times by using absolute ethyl alcohol and deionized water respectively, drying the precipitates for 4h at 100 ℃, sintering the precipitates for 3h at 500 ℃ in a box-type resistance furnace, annealing for 120min at 200 ℃ in a nitrogen atmosphere at the cooling rate of 30 ℃/min to obtain the nano-material. In the embodiment, the average particle size of the optical nano material is about 30nm, and through detection, the titanium dioxide in the optical nano material has two crystal forms of anatase and rutile, and the specific surface area is 657m2The photoresponse range is 300-810 nm.
Example 3
First, 8mL Ti (OBu)4Adding the mixture into 40mL of absolute ethyl alcohol, stirring and dissolving until the mixture is uniform to obtain a solution A; dissolving 5mL of 2mol/L ammonia water in 20mL of absolute ethyl alcohol, sequentially dripping 1mL of glacial acetic acid and 5mL of deionized water, and uniformly stirring to obtain a solution B (the pH value is 3-4); dropwise adding the solution B into the solution A while stirring, stirring for 30min to obtain a mixed solution, transferring the mixed solution into a 200mL polytetrafluoroethylene stainless steel reaction kettle, and placing into the kettleAnd (3) drying in an oven, carrying out heat treatment at 200 ℃ for 7h, cooling, carrying out centrifugal separation on the liquid, washing the precipitate for 3 times by using absolute ethyl alcohol and deionized water respectively, drying the precipitate for 4h at 100 ℃, sintering the precipitate for 2h at 700 ℃ in a box-type resistance furnace, annealing for 100min at 400 ℃ in a nitrogen atmosphere, and cooling at the rate of 50 ℃/min to obtain the optical nano material. In this embodiment, the average particle size of the optical nano material is about 21nm, and through detection, the titanium dioxide in the optical nano material has two crystal forms of anatase and rutile, and the specific surface area is 724m2The photoresponse range is 300-830 nm. Although the titanium dioxide in the optical nano-materials of examples 1-3 contains anatase and rutile crystal forms, the ratio of anatase and rutile crystal forms is different due to the difference of annealing temperature and annealing time, the surface structures of the optical nano-materials are different, and the specific surface area is greatly different.
The light nano material prepared in the embodiment is used for treating black and odorous watercourses in certain places of Jilin, and the conditions before treatment are as follows: the width of the river surface is about 10m, the weeds in the slope protection on two sides are clustered, the condition of dumping garbage exists, the water surface covers floaters and emits peculiar smell, and the water quality indexes are as follows: ammonia nitrogen about 30mg/L, CODCrAbout 150 mg/L. After garbage and weeds on two sides of a river channel and river surface floating objects are cleaned and added according to the addition amount of 0.03g/L, after 1 month, the transparency of a water body is gradually improved and odor disappears after treatment, the pH value is stabilized between 7.0 and 7.5, the dissolved oxygen is about 4.5mg/L, the ammonia nitrogen is maintained below 1mg/L, and the COD (chemical oxygen demand) is maintainedCrThe water quality of the water body reaches III-class water quality standards of the surface water environment of the people's republic of China (GB 3838-.
Example 4
First, 8mL Ti (OBu)4Adding the mixture into 40mL of absolute ethyl alcohol, stirring and dissolving until the mixture is uniform to obtain a solution A; dissolving 3mL of 2mol/L ammonia water in 20mL of absolute ethyl alcohol, sequentially dripping 1mL of glacial acetic acid and 5mL of deionized water, and uniformly stirring to obtain a solution B (the pH value is 3-4); dropwise adding the solution B into the solution A while stirring, stirring for 25min to obtain a mixed solution, and transferring the mixed solution into a 200mL polytetrafluoroethylene stainless steel reaction kettlePutting the mixture into an oven, carrying out heat treatment at 200 ℃ for 10h, cooling, carrying out centrifugal separation on the liquid, washing the precipitate for 3 times by using absolute ethyl alcohol and deionized water respectively, then drying the precipitate for 4h at 100 ℃, sintering the precipitate for 3h at 650 ℃ in a box-type resistance furnace, annealing for 100min at 400 ℃ in a nitrogen atmosphere, and cooling at the rate of 30 ℃/min to obtain the optical nano material. In this example, the average particle size of the optical nano material is about 25nm, and through detection, the titanium dioxide in the optical nano material has two crystal forms of anatase and rutile, and the specific surface area is 751m2The photoresponse range is 320-810 nm.
Comparative example 1
The difference from example 1 is only that the annealing treatment is not performed after sintering.
The average particle diameter of the optical nano material in the comparative example is 50-90nm, and through detection, the titanium dioxide in the optical nano material only contains anatase crystal form, and the specific surface area is 287m2The photoresponse range is 380-470 nm.
The optical nano material prepared by the comparative example is used for treating black and odorous watercourses of Jilin places, and the conditions before treatment are as follows: the width of the river surface is about 5m, the weeds in the slope protection on two sides are clustered, the condition of dumping garbage exists, the water surface covers floaters and emits peculiar smell, and the water quality indexes are as follows: dissolved oxygen of about 1.4mg/L, ammonia nitrogen of about 30mg/L, CODCrAbout 150 mg/L. After garbage and weeds on two sides of a river channel and river surface floating objects are cleaned and added according to the adding amount of 30g/L, after 8 months, the transparency of a water body is gradually improved and odor disappears after treatment, the pH value is stabilized between 7.5 and 8.5, the dissolved oxygen is about 2.1mg/L, the ammonia nitrogen is about 12mg/L, and the COD isCrAbout 35 mg/L.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.
Claims (7)
1. A preparation method of a light nano material for treating black and odorous water is characterized by comprising the following steps:
(1) adding tetrabutyl titanate into absolute ethyl alcohol, and stirring uniformly to obtain a solution A;
(2) dissolving ammonia water in absolute ethyl alcohol, sequentially dripping glacial acetic acid and deionized water, and uniformly stirring to obtain a solution B;
(3) dropwise adding the solution B into the solution A while stirring to obtain a mixed solution;
(4) carrying out heat treatment on the mixed solution, cooling, centrifuging, cleaning a precipitate and drying;
(5) sintering the dried precipitate, and then carrying out annealing treatment.
2. The preparation method according to claim 1, wherein the volume ratio of tetrabutyl titanate to absolute ethyl alcohol in the step (1) is (1-2): 5.
3. the preparation method according to claim 1, wherein the concentration of the ammonia water in the step (2) is 2mol/L, and the volume ratio of the ammonia water, the absolute ethyl alcohol, the glacial acetic acid and the deionized water is (3-5): 20: 1: 5.
4. the method as claimed in claim 1, wherein the heat treatment temperature in step (4) is 150 ℃ to 200 ℃ and the heat treatment time is 7-10 h.
5. The method as claimed in claim 1, wherein the sintering temperature in step (5) is 450-700 ℃ and the sintering time is 2-3 h.
6. The method as claimed in claim 1, wherein the annealing temperature in step (5) is 200-400 ℃, the annealing time is 100-120min, the temperature reduction rate is 30-50 ℃/min, and the annealing atmosphere is nitrogen.
7. The optical nano-material for treating black and odorous water prepared by the preparation method according to any one of claims 1 to 6, wherein the average particle size of the optical nano-material is 20 to 40 nm.
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