CN113582226B - Preparation method of light nano material for treating black and odorous water body - Google Patents
Preparation method of light nano material for treating black and odorous water body Download PDFInfo
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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 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000000243 solution Substances 0.000 claims abstract description 33
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 14
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 11
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- 238000010438 heat treatment Methods 0.000 claims abstract description 11
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- 238000001035 drying Methods 0.000 claims abstract description 7
- 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
- 230000003287 optical effect Effects 0.000 claims description 29
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- 238000000034 method Methods 0.000 claims description 8
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- 238000005406 washing Methods 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 238000010335 hydrothermal treatment Methods 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
- 239000011574 phosphorus Substances 0.000 abstract description 7
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 7
- 238000004140 cleaning Methods 0.000 abstract description 6
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- 238000009395 breeding Methods 0.000 abstract description 3
- 230000001488 breeding effect Effects 0.000 abstract description 3
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 34
- 241000196324 Embryophyta Species 0.000 description 12
- 239000004408 titanium dioxide Substances 0.000 description 10
- 239000010813 municipal solid waste Substances 0.000 description 9
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- 239000013049 sediment Substances 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000011651 chromium Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- -1 polychlorinated biphenyl compounds Chemical class 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 229910010413 TiO 2 Inorganic materials 0.000 description 5
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 5
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- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
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- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
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- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/39—Photocatalytic properties
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
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- 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
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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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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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
- C02F2303/02—Odour removal or prevention of malodour
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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
- C02F2305/08—Nanoparticles or nanotubes
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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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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention discloses a preparation method of a light nano material for treating black and odorous water body, which belongs to the technical field of black and odorous water body treatment and comprises the following steps: adding tetrabutyl titanate into absolute ethyl alcohol, and stirring until the mixture is uniform 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, and stirring the solution A while dropwise adding to obtain a mixed solution; carrying out heat treatment on the mixed solution, cooling, centrifuging, cleaning the precipitate, and drying; the dried precipitate is sintered and then 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 blue algae breeding 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, urban surface water is seriously polluted, and the waste water discharge rate is increased rapidly and the total amount of urban domestic sewage is increased continuously from the aspect of overall situation. Because the domestic sewage treatment rate is low (about only 20% -30%), most domestic sewage is directly or indirectly discharged into urban river channels without treatment, and a large amount of industrial wastewater is discharged, so that the oxygen-consuming organic pollutants and nitrogen and phosphorus content of the river channels are high, the eutrophication of the water body is serious to black and odorous, and the aquatic plants such as blue algae, water hyacinth and water peanut are explosively propagated, so that the river channel water environment is seriously polluted, and the ecological degradation of the river channel water is accelerated. The serious deterioration of urban river environment not only affects the sustainable development of urban economy, but also seriously affects the health and life of people due to bad water quality and bad ozone smoking.
At present, a microorganism strengthening technology, a biological film technology and a plant purifying technology are adopted to treat black and odorous water bodies, but the main problems in the method are as follows: (1) river water quality is still poor, and the landscape quality is not high: the problems of turbidity, high nitrogen and phosphorus content, low dissolved oxygen, low transparency and the like of river water commonly exist, the number of V-class and inferior V-class river channels is still about 90 percent, and the treated river channels have more black and odorous rebound phenomena. River landscapes and water quality degradation during rainy days, particularly during stormwater, are common and prominent problems. (2) a large amount of contaminated sediment sludge: although sediment dredging is widely applied to small-sized river management as one of the leading measures for river channel remediation, investigation results show that the rapid accumulation of the sediment in the river channel after dredging is still very common, and the main reason is that the intensity of the sediment (sewage and garbage) is high and the hydrodynamic force of river network is seriously insufficient. The surface layer sediment of the black and odorous river channel has high contents of organic matters, heavy metals, nitrogen, phosphorus and the like, and the decomposition and the re-suspension of the sediment not only can aggravate the pollution of overlying river water, but also can consume a large amount of DO. Both the sediment and the river water have certain acute, subacute and genetic toxicity, and the persistent toxic pollutants are enriched in organisms to different degrees along the food chain, so that the toxicity of the sediment is higher than that of the river water. The influence of the dredging process of the polluted substrate sludge on the water quality and landscape of river water, and the on-site stabilization and restoration of the substrate after dredging are the problems to be solved in the deep treatment of the black and odorous river channel. (3) degradation and even collapse of the river water ecosystem: the aquatic community of the urban black and odorous river is incomplete in structure and function, the number of species, especially large-scale aquatic organisms, is poor, individuals are miniaturized, and most of the species are pollution-resistant; the biological diversity is low, the colony type is mainly single-excellent colony and is relatively concentrated on the surface layer of the water body, and the substrate is bad in habitat and is not suitable for growth and reproduction of benthonic animals such as snails, clams and the like. Except for a very small number of small river channels (which are subjected to ecological restoration treatment in recent years), all submerged plants and macrophytes in almost all urban rivers at present die. The ecological chain of the black and odorous river channel is extremely degraded, and the output, transfer and purification effects of pollutants cannot be completed, so that the pollutants are seriously blocked and vicious circle is caused. (4) river water self-cleaning capability is poor, algal bloom bursts: river water flow speed is slow, hydrodynamic force is insufficient, self-cleaning capability is not strong, and especially, the self-cleaning capability of a closed small river (with one end broken or all cut off) water body is poor, so that a large amount of planktonic algae are bred, and algae bloom seasonally erupts and emits fishy smell. The large-scale breeding of water hyacinth, water peanut, duckweed, algal bloom and the like is a problem which needs to be solved in the deep treatment of urban rivers for a long time.
Accordingly, in order to solve the above-mentioned problems, it is necessary to provide a new method for treating black and odorous water bodies.
Disclosure of Invention
The invention aims to provide a preparation method of a light nano material for treating black and odorous water body, which improves the treatment capacity of the black and odorous water body.
In order to achieve the above object, the present invention provides the following solutions:
the invention provides a preparation method of a light nano material for treating black and odorous water bodies, which comprises the following steps:
(1) Adding tetrabutyl titanate into absolute ethyl alcohol, and stirring until the mixture is uniform 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, and stirring the solution A while dropwise adding to obtain a mixed solution;
(4) Carrying out heat treatment on the mixed solution, cooling, centrifuging, cleaning the 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) in sequence: 20:1:5.
further, the heat treatment temperature in the step (4) is 150-200 ℃, and the heat treatment time is 7-10h.
Further, the sintering temperature in the step (5) is 450-700 ℃ and the sintering time is 2-3h.
Further, the annealing temperature in the step (5) is 200-400 ℃, the annealing time is 100-120min, the cooling rate is 30-50 ℃/min, and the annealing atmosphere is nitrogen.
Due to TiO 2 The forbidden bandwidth of the semiconductor is wider than 3.2eV, the corresponding wavelength is 387nm, the ultraviolet is in the ultraviolet region, the ultraviolet only occupies 3% -4% of sunlight on the earth surface, and most of visible light (energy occupies about 45%) in the solar spectrum is not effectively utilized. In the present invention, the crystallinity without annealing is very low, being substantially amorphous; after annealing treatment at 200-400 ℃, the material is in a polycrystalline state, and after annealing treatment, N mainly exists in the form of substitution in TiO 2 In the polycrystalline structure, a small amount of the gap N may form a small amount of Ti-N bonds with Ti, and doped N may also overflow into the chamber due to the stronger strength of the Ti-O bonds 2 It is difficult to replace O in Ti-O bond, so the optical nano material contains Ti-N bond and Ti-O bond at the same time, contains mixed crystal of anatase and rutile, and the hybridization of N2 p orbit and O2 p orbit makes TiO 2 Is reduced due to N substitution to increase TiO 2 Is effective in improving the visible light activity of the light source. Therefore, the invention provides an optical nano material, and nitrogen can replace a small amount of lattice oxygen to enable TiO 2 The band gap of the black and odorous water body is narrowed, the ultraviolet light activity is not reduced, and the black and odorous water body has visible light activity, so that the treatment effect on 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 0.03-0.05g/L.
Under the irradiation of light, the light nano material is excited to generate electron-hole pairs, which are high-energy particles and are mixed with surrounding water and oxygenAfter the reaction, a system with extremely strong oxidation-reduction capability is formed, and the organic matters adsorbed on the surface of the system can be rapidly degraded into CO 2 And H 2 Small molecules such as O and the like can degrade various organic pollutants including polycyclic aromatic hydrocarbon and polychlorinated biphenyl compounds which are difficult to degrade, and can reduce inorganic pollutants such as cyanogen, chromium and the like contained in wastewater.
Titanium dioxide photocatalytic efficiency is achieved by generating reactive oxygen species and singlet oxygen species, which can generate superoxide and hydroxyl radicals upon irradiation with both ultraviolet and visible light. However, when the size of the titanium dioxide ions is as small as a few nanometers, the photocatalytic activity is lost, and because charges and holes cannot be formed on the surfaces of the particles, the average particle size is controlled to be 20-40nm through adjustment of the preparation method, so that the probability of titanium dioxide charge/hole recombination is reduced, meanwhile, the surface structure of the optical nano material is rough, the adhesion force of pollutants can be increased, the pollutants are 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 in-situ degradation of the pollutants in complex environments 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 nano particles widens the energy gap of a semiconductor, the conduction band potential becomes more negative, and the valence band potential becomes more positive, so that the optical nano material has stronger oxidation-reduction capability. In addition, the particle size of the particles is smaller (the average particle size is 20-40 nm), so that the probability of electron and hole recombination is smaller, the charge separation is more 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 nanometer material can remove pollutants (suspended particles, dissolved phosphorus and the like) in water, promote the rapid purification of pollutants (organic matters, nitrogen, phosphorus and the like), kill or control blue algae breeding, and improve the transparency of water.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions 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. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, 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 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 invention described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present invention. The specification and examples of the present invention are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
Example 1
First 8mL Ti (OBu) 4 Adding the mixture into 40mL of absolute ethyl alcohol, stirring and dissolving until the mixture is uniform to obtain 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 stirringUniformity, giving solution B (ph=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 into a baking oven, performing heat treatment at 150 ℃ for 10h, centrifugally separating the liquid after cooling, washing the precipitate with absolute ethyl alcohol and deionized water for 3 times respectively, drying the precipitate at 100 ℃ for 4h, sintering the precipitate in a box-type resistance furnace at 450 ℃ for 3h, annealing at 300 ℃ for 120min under nitrogen atmosphere, and cooling at 30 ℃/min to obtain the optical nano material. In the embodiment, the average grain diameter of the optical nano material is about 38nm, and the titanium dioxide in the optical nano material has two crystal forms of anatase and rutile and has a specific surface area of 626m 2 And/g, the light response range is 310-810nm.
The optical nano material prepared in the embodiment is used for treating black and odorous river channels in Jilin places, and the conditions before treatment are as follows: river surface narrowing, river bed siltation, water falling, weed clustering, poor self-cleaning capability of water body and most of time flow interruption; the bridge and culvert construction standard in the water system is low, the water flow section is smaller, the culvert bottom is high, and the flowing water is unsmooth. After the river garbage, weeds and river surface floaters are cleaned, the water transparency is gradually improved and the odor disappears after the treatment after 2 months after the river garbage, the weeds and the river surface floaters are added according to the adding amount of 0.05g/L, the pH value is stabilized between 7.0 and 7.5, the dissolved oxygen is about 4.1mg/L, the ammonia nitrogen is kept below 2mg/L, and the COD is maintained Cr The water quality of the water body is maintained below 30mg/L, reaches the III water quality standard of the surface water environment quality standard of the people's republic of China (GB 3838-2002), and can be maintained for more than 2 years.
Example 2
First 16mL Ti (OBu) 4 Adding the mixture into 40mL of absolute ethyl alcohol, stirring and dissolving until the mixture is uniform to obtain solution A; dissolving 4mL of ammonia water with the concentration of 2mol/L in 20mL of absolute ethyl alcohol, sequentially dripping 1mL of glacial acetic acid and 5mL of deionized water, and uniformly stirring to obtain solution B (pH=3-4); dropwise adding solution B into solution A, stirring while dropwise adding, stirring for 30min to obtain mixed solution, transferring the mixed solution into 200mL polytetrafluoroethylene stainless steel reaction kettle, placing into oven, heat treating at 180deg.C for 8 hr, cooling, centrifuging to separate liquidAnd (3) separating, washing the precipitate with absolute ethyl alcohol and deionized water for 3 times respectively, drying the precipitate at 100 ℃ for 4 hours, sintering the precipitate at 500 ℃ for 3 hours in a box-type resistance furnace, annealing the precipitate at 200 ℃ for 120 minutes in a nitrogen atmosphere, and obtaining the optical nano material at a cooling rate of 30 ℃/min. In the embodiment, the average grain diameter of the optical nano material is about 30nm, and the titanium dioxide in the optical nano material has two crystal forms of anatase and rutile and has a specific surface area of 657m 2 And/g, the light response range is 300-810nm.
Example 3
First 8mL Ti (OBu) 4 Adding the mixture into 40mL of absolute ethyl alcohol, stirring and dissolving until the mixture is uniform to obtain solution A; dissolving 5mL of ammonia water with the concentration of 2mol/L in 20mL of absolute ethyl alcohol, sequentially dripping 1mL of glacial acetic acid and 5mL of deionized water, and uniformly stirring to obtain solution B (pH=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 into a baking oven, performing heat treatment at 200 ℃ for 7h, centrifugally separating the liquid after cooling, washing the precipitate with absolute ethyl alcohol and deionized water for 3 times respectively, drying the precipitate at 100 ℃ for 4h, sintering the precipitate in a box-type resistance furnace at 700 ℃ for 2h, annealing at 400 ℃ for 100min under nitrogen atmosphere, and cooling at 50 ℃/min to obtain the optical nano material. In the embodiment, the average grain diameter of the optical nano material is about 21nm, and the titanium dioxide in the optical nano material has two crystal forms of anatase and rutile and the specific surface area is 724m through detection 2 And/g, the light response range is 300-830nm. Although the titanium dioxide in the optical nanomaterial of examples 1 to 3 contains both anatase and rutile, the ratio of anatase and rutile is different due to the difference of the annealing temperature and the annealing time, the surface structures of the optical nanomaterial are different, and the specific surface areas are greatly different.
The optical nano material prepared in the embodiment is used for treating black and odorous river channels in Jilin places, and the conditions before treatment are as follows: its river surface width is about 10m, and both sides bank protection weeds are clustered and have rubbish to empty the condition, and the surface of water covers floater, gives off the peculiar smell, and water quality index is as follows: ammonia nitrogen about 30mg/L, COD Cr About 150 mg-L. After the garbage weeds and the river surface floaters on the two sides of the river channel are cleaned, the garbage weeds and the river surface floaters are added according to the adding amount of 0.03g/L, after 1 month, the transparency of the water body is gradually improved, the odor disappears after the treatment, the pH value is stabilized between 7.0 and 7.5, the dissolved oxygen is about 4.5mg/L, the ammonia nitrogen is kept below 1mg/L, and the COD is maintained Cr The water quality of the water body reaches the III water quality standard of the surface water environment standard of the people's republic of China (GB 3838-2002) and can be maintained for more than 2 years.
Example 4
First 8mL Ti (OBu) 4 Adding the mixture into 40mL of absolute ethyl alcohol, stirring and dissolving until the mixture is uniform to obtain solution A; dissolving 3mL of ammonia water with the concentration of 2mol/L in 20mL of absolute ethyl alcohol, sequentially dripping 1mL of glacial acetic acid and 5mL of deionized water, and uniformly stirring to obtain solution B (pH=3-4); dropwise adding the solution B into the solution A, stirring while dropwise adding, stirring for 25min after dropwise adding to obtain a mixed solution, transferring the mixed solution into a 200mL polytetrafluoroethylene stainless steel reaction kettle, putting into a baking oven, performing heat treatment at 200 ℃ for 10h, centrifugally separating the liquid after cooling, washing the precipitate with absolute ethyl alcohol and deionized water for 3 times respectively, drying the precipitate at 100 ℃ for 4h, sintering the precipitate in a box-type resistance furnace at 650 ℃ for 3h, annealing at 400 ℃ for 100min under nitrogen atmosphere, and cooling at 30 ℃/min to obtain the optical nano material. In the embodiment, the average grain diameter of the optical nano material is about 25nm, and the titanium dioxide in the optical nano material has two crystal forms of anatase and rutile and the specific surface area is 751m through detection 2 And/g, the light response range is 320-810nm.
Comparative example 1
The difference from example 1 is that no annealing treatment is performed after sintering.
The average grain diameter of the optical nano material in the comparative example is 50-90nm, and the titanium dioxide in the optical nano material only contains anatase crystal form and the specific surface area is 287m 2 And/g, the light response range is 380-470nm.
The optical nano material prepared in the comparative example is used for treating black and odorous river channels in Jilin places, and the conditions before treatment are as follows: the river surface width is about 5m, and the weeds on the two sides of the river surface are clustered and storedUnder the condition of dumping garbage, the water surface is covered with floaters and gives off peculiar smell, and the water quality indexes are as follows: dissolved oxygen of about 1.4mg/L, ammonia nitrogen of about 30mg/L, COD Cr About 150mg/L. After the garbage weeds and the river surface floaters on the two sides of the river channel are cleaned, the water transparency is gradually improved and the odor disappears after the treatment after 8 months after the garbage weeds and the river surface floaters are added according to the adding amount of 30g/L, 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 is about 12mg/L Cr About 35mg/L.
The above embodiments are only illustrative of the preferred embodiments of the present invention and are not intended to limit the scope of the present invention, and various modifications and improvements made by those skilled in the art to the technical solutions of the present invention should fall within the protection scope defined by the claims of the present invention without departing from the design spirit of the present invention.
Claims (4)
1. The preparation method of the optical nano material for treating the black and odorous water body is characterized by comprising the following steps of:
(1) Adding tetrabutyl titanate into absolute ethyl alcohol, and stirring until the mixture is uniform 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, and stirring the solution A while dropwise adding to obtain a mixed solution;
(4) Carrying out heat treatment on the mixed solution, cooling, centrifuging, washing and drying the precipitate, wherein the heat treatment temperature is 150-200 ℃, the heat treatment time is 7-10h, and the heat treatment is hydrothermal treatment;
(5) Sintering the dried precipitate, and then carrying out annealing treatment, wherein the sintering temperature is 450-700 ℃ and the sintering time is 2-3h; the annealing temperature is 200-400 ℃, the annealing time is 100-120min, the cooling rate is 30-50 ℃/min, and the annealing atmosphere is nitrogen;
the average grain diameter of the light nanometer material is 20-40nm.
2. The method according to claim 1, wherein the volume ratio of tetrabutyl titanate to absolute ethanol in the step (1) is (1-2): 5.
3. the 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) in sequence: 20:1:5.
4. a photo nanomaterial for treating black and odorous water body prepared by the preparation method according to any one of claims 1 to 3, characterized in that the average particle size of the photo nanomaterial is 20 to 40nm.
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