CN117886393A - Method for degrading cultivation wastewater by catalytic oxidation - Google Patents
Method for degrading cultivation wastewater by catalytic oxidation Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 27
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 25
- 230000003647 oxidation Effects 0.000 title claims abstract description 24
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 24
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- Treatment Of Water By Oxidation Or Reduction (AREA)
- Physical Water Treatments (AREA)
Abstract
The invention discloses a method for degrading aquaculture wastewater by catalytic oxidation, which belongs to the technical field of wastewater treatment and comprises the following steps: filtering insoluble substances from the culture wastewater to be treated, then adjusting the pH to be neutral or acidic, adding a photocatalyst, stirring and dispersing, keeping the temperature of the culture wastewater constant, fully stirring under the illumination condition, and carrying out photocatalytic oxidation degradation reaction on pollutants in the culture wastewater; wherein the photocatalyst comprises an alkali metal based tungsten bronze material; the invention takes the tungsten bronze material based on alkali metal as the photocatalyst, and can realize the activation by directly utilizing the dissolved oxygen in the water body and the oxidative degradation of organic pollutants or ammonia nitrogen in the water under the conditions of room temperature, no special additive and full spectrum irradiation.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a method for degrading aquaculture wastewater by catalytic oxidation.
Background
The livestock and poultry breeding industry is an important industry for guaranteeing the civil level, the livestock and poultry breeding amount and consumption amount of China are the first world, and the livestock and poultry breeding wastewater pollution becomes the most important non-point source pollution of China. The livestock and poultry breeding wastewater mainly comprises urine, feces and breeding house flushing water, the concentration of organic matters in the wastewater is high, the COD (chemical oxygen demand) of the wastewater is 5000-13000 mg/L, BOD and is 5000-6000 mg/L, suspended matters are more, the SS is 17000-20000 mg/L, the ammonia nitrogen content is high, the ammonia nitrogen content is 600-1000 mg/L, and the odor is large. The cultivation wastewater belongs to high-concentration organic wastewater rich in a large amount of pathogens, is directly discharged into a water body or is unsuitable to be stored in a place, is washed by rainwater and enters the water body, and can possibly cause serious deterioration of the quality of surface water or underground water. Because the leaching capacity of the livestock and poultry manure is very high, nitrogen, phosphorus, water-soluble organic matters and the like in the manure are very large, and if the livestock and poultry manure is not properly treated, the livestock and poultry manure enters an underground water layer to pollute underground water through surface runoff and infiltration. The influence on the surface water is mainly expressed in that after a large amount of organic matters enter the water body, the decomposition of the organic matters consumes a large amount of dissolved oxygen in the water body so as to cause the water body to be odorized; when the dissolved oxygen in the water body is greatly reduced, a large amount of organic substances can be continuously decomposed under the anaerobic condition, and toxic gases such as methane, hydrogen sulfide and the like can be generated during the decomposition, so that a large amount of aquatic organisms die; a large amount of suspended matters in the wastewater can cause turbidity of water, reduce photosynthesis of algae in the water, limit normal activities of aquatic organisms, and gradually death aquatic organisms sensitive to organic pollution, so that oxygen deficiency at the bottom of the water is further aggravated, and the assimilation capability of the water is reduced; the nitrogen and the phosphorus can cause the water body to be eutrophicated, the concentration of nitrate and nitrite in the water body is too high as a result of the eutrophication, people and livestock can cause poisoning if drinking for a long time, and the growth and mass propagation of some toxic algae can discharge a large amount of toxins in the water body, so that a large amount of aquatic animals die, and the ecological balance of the water body is seriously destroyed; some germs, viruses, etc. in the feces and urine flow with water, possibly causing the transmission of certain epidemic diseases, etc. It has now been found that part of the ground water of the breeding area is contaminated, which exacerbates the breeding epidemic prevention pressure; wherein, the related reports on new pollutants such as hormone, livestock antibiotics and the like in the water body also sound alarms to human beings, the pollution situation of livestock and poultry cultivation is severe, and the health of human beings can be possibly endangered.
At present, the treatment method for large-scale livestock and poultry wastewater at home and abroad mainly comprises two main types of comprehensive utilization and treatment standard emission. Comprehensive utilization is a good way for multi-level utilization of biomass energy, construction of ecological agriculture and guarantee of sustainable development of agriculture. However, at present, due to the lag of the feeding management mode of livestock and poultry farms in China and the inadequacy of anaerobic treatment before comprehensive utilization, a plurality of problems are often caused in the process of comprehensive utilization of livestock and poultry manure water, such as large wastewater production amount, complex components, high pollutant concentration after treatment, large dilution water amount, influence of seasonal irrigation and the like; the treatment reaches the standard, and the pollutants are degraded by adopting oxidation technologies such as electrochemical oxidation, ozone oxidation, photocatalytic oxidation and the like, wherein the photocatalytic oxidation method has the advantages of better utilizing light energy, short reaction time, mild conditions and the like, but the current photocatalyst has the problems of short excitation wavelength, small excitation window, low degradation efficiency, high energy density of a required light source and the like.
Disclosure of Invention
In view of at least one of the above problems, the present invention provides a method for catalytic oxidative degradation of aquaculture wastewater.
The aim of the invention is realized by adopting the following technical scheme:
a method for degrading cultivation wastewater by catalytic oxidation, which comprises the following steps of;
filtering insoluble substances from the culture wastewater to be treated, then adjusting the pH to be neutral or acidic, adding a photocatalyst, stirring and dispersing, keeping the temperature of the culture wastewater constant, fully stirring under the illumination condition, and carrying out photocatalytic oxidation degradation reaction on pollutants in the culture wastewater;
wherein the photocatalyst comprises an alkali metal-based tungsten bronze material, and the preparation method comprises the following steps:
weighing tungsten hexacarbonyl, adding the tungsten hexacarbonyl into absolute ethyl alcohol, fully stirring and dissolving to obtain tungsten hexacarbonyl solution, adding ethanol solution of cesium nitrate and rubidium nitrate, stirring and mixing again until the mixture is uniform, transferring the mixed solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, carrying out heat preservation reaction for 20-30h at the autogenous pressure of 200-240 ℃, carrying out self-cooling to room temperature after the reaction is finished, separating precipitate, washing the precipitate with deionized water and absolute ethyl alcohol respectively, carrying out vacuum drying, heating to 500-600 ℃ under the reducing atmosphere condition, carrying out heat preservation reaction for 1-2h, carrying out heat preservation reaction for 0.5-1h under the air atmosphere condition, carrying out cooling to obtain a light yellow product, carrying out heat preservation for 2-4h at the temperature of 160-180 ℃ after the light yellow product is mixed with thiourea, and carrying out cooling and grinding to obtain the product.
In some preferred embodiments, the mass ratio of the tungsten hexacarbonyl to the cesium nitrate to the rubidium nitrate is 1: (0.5-0.8): (0.2-0.5); the mass ratio of the light yellow product to the thiourea is (1-3): 1.
in some preferred embodiments, the pH of the aquaculture wastewater is adjusted to 6-7; the constant temperature of the culture wastewater is 25-50 ℃.
In some preferred embodiments, the alkali metal-based tungsten bronze material has a grinding particle size of 0.1 to 100 μm and is added to the cultivation wastewater in an amount of 10 to 100mg/L.
In some preferred embodiments, the illumination condition is ultraviolet light, sunlight or xenon lamp illumination, and the light source has an optical power density of 50-300mW/cm 2 The distance between the light source and the liquid level of the cultivation wastewater is 10-50cm.
In some preferred embodiments, the contaminants include ammonia nitrogen and/or organic contaminants including antibiotics.
In some preferred embodiments, the concentration of the ammonia nitrogen in the aquaculture wastewater is between 0 and 200mg/L and the concentration of the organic contaminant is between 0 and 2000mg/L.
In some preferred embodiments, the photocatalyst further comprises a strengthening agent, and the method of preparing the strengthening agent comprises the steps of:
(1) Weighing triphenylamine and dissolving the triphenylamine in a dimethylformamide solvent, adding N-bromosuccinimide under ice water bath condition, fully stirring and mixing, preserving heat and reacting for 3-5 hours, concentrating under reduced pressure after the reaction is finished, washing the product with deionized water and saturated saline water respectively, removing unreacted reactants through a silica gel column to obtain a brominated product, dissolving the brominated product in the tetrahydrofuran solvent, adding butyl lithium solution under the conditions of protective atmosphere and ice water bath, preserving heat and stirring and reacting for 1-2 hours, adding isopropanol pinacol borate, continuing to preserving heat and stirring and reacting for 1-2 hours, stirring and reacting for 6-10 hours at normal temperature, adding cold deionized water after the reaction is finished, diluting a reaction system, concentrating after diethyl ether extraction, removing unreacted reactants through the silica gel column, and drying to obtain a precursor product;
(2) And (3) dissolving the precursor product in a toluene solvent under a protective atmosphere, adding 2, 3-bis (4-bromophenyl) -2-butenedinitrile and tetraethylammonium hydroxide, fully stirring and mixing, adding tribenzylidene acetone dipalladium and tris (o-methylphenyl) phosphorus, stirring and reacting for 24-36h under the protective atmosphere, cooling to room temperature after the reaction is finished, adding methanol to dilute a reaction system, separating and washing precipitate, and drying to obtain the strengthening agent.
In some preferred embodiments, the mass ratio of the triphenylamine to the N-bromosuccinimide in step (1) is 1: (1.4-1.5), the mass ratio of the bromination product to the isopropanol pinacol borate is 1: (1.4-1.5); the mass ratio of the precursor product to the 2, 3-bis (4-bromophenyl) -2-butenedinitrile, the tetraethylammonium hydroxide, the tribenzylideneacetone dipalladium, the tris (o-methylphenyl) phosphorus in step (2) is 1: (0.76-0.79): (0.25-0.27): (0.02-0.03): (0.05-0.08).
In some preferred embodiments, the mass ratio of the alkali metal-based tungsten bronze material to the strengthening agent is 1: (0.1-0.3).
The beneficial effects of the invention are as follows:
aiming at the problems of short excitation wavelength, low catalytic degradation efficiency, high energy density of a light source and the like of the current photocatalyst, the invention takes the tungsten bronze material based on alkali metal as the photocatalyst, has mild degradation condition and high degradation efficiency, can effectively degrade the cultivation wastewater, and particularly, the invention obtains good photocatalytic performance by compounding cesium and rubidium on the basis of the alkali metal tungsten bronze and then carrying out thio doping with thiourea, which can be realized in the following wayUnder the condition of room temperature, the dissolved oxygen in the water body is directly utilized to activate and oxidize and degrade organic pollutants or ammonia nitrogen in the water without special additives and full spectrum irradiation; furthermore, the invention also adds an organic conjugated polymer with photosensitive function as a light absorption enhancer on the basis of the tungsten bronze photocatalyst based on alkali metal, which is polymerized by butenedinitrile monomer based on triphenylamine, and has high singlet oxygen under the irradiation of sunlight based on good light stability and large specific surface area 1 O 2 ) The generation efficiency of the catalyst can be further improved, the required energy density of the light source can be reduced, and the catalytic oxidation efficiency of the catalyst under the sunlight condition can be further improved.
Detailed Description
The invention will be further described with reference to the following examples.
Example 1
A method for degrading cultivation wastewater by catalytic oxidation, which comprises the following steps of;
filtering insoluble matters from the culture wastewater to be treated, adjusting the pH to 6-7, wherein the concentration of ammonia nitrogen in the adjusted wastewater is 157mg/L, and the COD is 400mg/L; adding photocatalyst, stirring for dispersion, wherein the addition amount is 70mg/L, the temperature of the cultivation wastewater is kept to be 40+/-5 ℃, the cultivation wastewater is fully stirred under the illumination condition of ultraviolet light, sunlight or xenon lamp, and the optical power density of a light source is 100mW/cm 2 The distance between the light source and the liquid level of the cultivation wastewater is 30cm, and the photocatalytic oxidation degradation reaction is carried out on pollutants in the cultivation wastewater;
wherein, the photocatalyst is tungsten bronze material based on alkali metal, and the preparation method comprises the following steps:
weighing tungsten hexacarbonyl and adding the tungsten hexacarbonyl into absolute ethyl alcohol, fully stirring and dissolving the tungsten hexacarbonyl to obtain tungsten hexacarbonyl solution, adding an ethanol solution of cesium nitrate and rubidium nitrate, stirring and mixing the solution again to be uniform, transferring the mixed solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, carrying out heat preservation reaction for 24 hours at the autogenous pressure of 220 ℃, carrying out self-cooling to room temperature after the reaction is finished, separating precipitate, washing the precipitate with deionized water and absolute ethyl alcohol respectively, carrying out vacuum drying, heating to 550 ℃ under the condition of reducing atmosphere, carrying out heat preservation reaction for 1.5 hours, carrying out heat preservation reaction for 0.5 hour under the condition of air atmosphere, cooling to obtain a light yellow product, mixing the light yellow product with thiourea, carrying out heat preservation for 2 hours at 176 ℃, cooling, and grinding the mixture to obtain the photocatalyst with the particle size of 1-10 mu m;
the mass ratio of the tungsten hexacarbonyl to the cesium nitrate to the rubidium nitrate is 1:0.65:0.35; the mass ratio of the light yellow product to the thiourea is 1.8:1.
example 2
A method for degrading cultivation wastewater by catalytic oxidation, which comprises the following steps of;
filtering insoluble matters from the culture wastewater to be treated, adjusting the pH to 6-7, wherein the concentration of ammonia nitrogen in the adjusted wastewater is 157mg/L, and the COD is 400mg/L; adding photocatalyst, stirring for dispersion, wherein the addition amount is 70mg/L, the temperature of the cultivation wastewater is kept to be 40+/-5 ℃, the cultivation wastewater is fully stirred under the illumination condition of ultraviolet light, sunlight or xenon lamp, and the optical power density of a light source is 100mW/cm 2 The distance between the light source and the liquid level of the cultivation wastewater is 30cm, and the photocatalytic oxidation degradation reaction is carried out on pollutants in the cultivation wastewater;
wherein, the photocatalyst is tungsten bronze material based on alkali metal, and the preparation method comprises the following steps:
weighing tungsten hexacarbonyl and adding the tungsten hexacarbonyl into absolute ethyl alcohol, fully stirring and dissolving the tungsten hexacarbonyl to obtain tungsten hexacarbonyl solution, adding ethanol solution of cesium nitrate and rubidium nitrate, stirring and mixing the solution again to be uniform, transferring the mixed solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, carrying out heat preservation reaction for 24 hours at the autogenous pressure of 220 ℃, carrying out self-cooling to room temperature after the reaction is finished, separating precipitate, washing the precipitate with deionized water and absolute ethyl alcohol respectively, carrying out vacuum drying, heating to 550 ℃ under the condition of reducing atmosphere, carrying out heat preservation reaction for 1.5 hours, carrying out heat preservation reaction for 0.5 hour under the condition of air atmosphere, cooling to obtain a light yellow product, and grinding the light yellow product to the particle size of 1-10 mu m to obtain the tungsten hexacarbonyl;
the mass ratio of the tungsten hexacarbonyl to the cesium nitrate to the rubidium nitrate is 1:0.65:0.35.
example 3
A method for degrading cultivation wastewater by catalytic oxidation, which comprises the following steps of;
filtering insoluble matters from the culture wastewater to be treated, adjusting the pH to 6-7, wherein the concentration of ammonia nitrogen in the adjusted wastewater is 157mg/L, and the COD is 400mg/L; adding photocatalyst, stirring for dispersion, wherein the addition amount is 70mg/L, the temperature of the cultivation wastewater is kept to be 40+/-5 ℃, the cultivation wastewater is fully stirred under the illumination condition of ultraviolet light, sunlight or xenon lamp, and the optical power density of a light source is 100mW/cm 2 The distance between the light source and the liquid level of the cultivation wastewater is 30cm, and the photocatalytic oxidation degradation reaction is carried out on pollutants in the cultivation wastewater;
wherein the photocatalyst is a mixture of tungsten bronze material based on alkali metal and a reinforcing agent, and the mixing mass ratio of the photocatalyst is 1:0.19, the method for preparing the alkali metal-based tungsten bronze material is the same as in example 1, and the method for preparing the strengthening agent comprises the following steps:
(1) Weighing triphenylamine and dissolving the triphenylamine in a dimethylformamide solvent, adding N-bromosuccinimide under ice water bath condition, fully stirring and mixing, preserving heat and reacting for 4 hours, concentrating under reduced pressure after the reaction is finished, washing the product with deionized water and saturated saline water respectively, removing unreacted reactants (eluting with petroleum ether) through a silica gel column to obtain a brominated product, dissolving the brominated product in the tetrahydrofuran solvent, adding butyl lithium solution under the conditions of protective atmosphere and ice water bath, preserving heat and stirring and reacting for 1 hour, adding isopropanol pinacol borate, continuing to preserving heat and stirring and reacting for 1 hour, stirring and reacting for 8 hours at normal temperature, adding cold deionized water after the reaction is finished, diluting a reaction system, extracting with diethyl ether, concentrating, removing unreacted reactants (DCM/PE eluting with V/V of 1:1) through the silica gel column, and drying to obtain a precursor product;
the mass ratio of the triphenylamine to the N-bromosuccinimide is 1:1.45, the mass ratio of the bromination product to the isopropanol pinacol borate is 1:1.42;
(2) Dissolving the precursor product in toluene solvent under protective atmosphere, adding 2, 3-bis (4-bromophenyl) -2-butenedinitrile and tetraethylammonium hydroxide, fully stirring and mixing, adding tribenzylidene acetone dipalladium and tris (o-methylphenyl) phosphorus, stirring and reacting for 30 hours under protective atmosphere, cooling to room temperature after the reaction is finished, adding methanol to dilute a reaction system, separating and washing precipitate, and drying to obtain the enhancer;
the mass ratio of the precursor product to the 2, 3-bis (4-bromophenyl) -2-butenedinitrile, the tetraethylammonium hydroxide, the tribenzylideneacetone dipalladium, the tris (o-methylphenyl) phosphorus is 1:0.77:0.26:0.02:0.06.
example 4
A method for degrading cultivation wastewater by catalytic oxidation, which comprises the following steps of;
filtering insoluble matters from the culture wastewater to be treated, adjusting the pH to 6-7, wherein the concentration of ammonia nitrogen in the adjusted wastewater is 157mg/L, and the COD is 400mg/L; adding photocatalyst, stirring for dispersion, wherein the addition amount is 70mg/L, the temperature of the cultivation wastewater is kept to be 40+/-5 ℃, the cultivation wastewater is fully stirred under the illumination condition of ultraviolet light, sunlight or xenon lamp, and the optical power density of a light source is 100mW/cm 2 The distance between the light source and the liquid level of the cultivation wastewater is 30cm, and the photocatalytic oxidation degradation reaction is carried out on pollutants in the cultivation wastewater;
wherein the photocatalyst is the enhancer of example 3.
Example 5
A method for degrading cultivation wastewater by catalytic oxidation, which comprises the following steps of;
filtering insoluble matters from the culture wastewater to be treated, adjusting the pH to 6-7, wherein the concentration of ammonia nitrogen in the adjusted wastewater is 157mg/L, and the COD is 400mg/L; adding photocatalyst, stirring for dispersion, wherein the addition amount is 70mg/L, the temperature of the cultivation wastewater is kept to be 40+/-5 ℃, the cultivation wastewater is fully stirred under the illumination condition of ultraviolet light, sunlight or xenon lamp, and the optical power density of a light source is 100mW/cm 2 The distance between the light source and the liquid level of the cultivation wastewater is 30cm, and the photocatalytic oxidation degradation reaction is carried out on pollutants in the cultivation wastewater;
wherein the photocatalyst is a commercial titanium dioxide catalyst (P25).
Experimental example
The catalytic degradation efficiency of the catalytic degradation systems described in examples 1 to 5 under ultraviolet light, sunlight and xenon lamp illumination were measured respectively, and the measurement results are as follows:
finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
1. A method for degrading aquaculture wastewater by catalytic oxidation, which is characterized by comprising the following steps of;
filtering insoluble substances from the culture wastewater to be treated, then adjusting the pH to be neutral or acidic, adding a photocatalyst, stirring and dispersing, keeping the temperature of the culture wastewater constant, fully stirring under the illumination condition, and carrying out photocatalytic oxidation degradation reaction on pollutants in the culture wastewater;
wherein the photocatalyst comprises an alkali metal-based tungsten bronze material, and the preparation method comprises the following steps:
weighing tungsten hexacarbonyl, adding the tungsten hexacarbonyl into absolute ethyl alcohol, fully stirring and dissolving to obtain tungsten hexacarbonyl solution, adding ethanol solution of cesium nitrate and rubidium nitrate, stirring and mixing again until the mixture is uniform, transferring the mixed solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, carrying out heat preservation reaction for 20-30h at the autogenous pressure of 200-240 ℃, carrying out self-cooling to room temperature after the reaction is finished, separating precipitate, washing the precipitate with deionized water and absolute ethyl alcohol respectively, carrying out vacuum drying, heating to 500-600 ℃ under the reducing atmosphere condition, carrying out heat preservation reaction for 1-2h, carrying out heat preservation reaction for 0.5-1h under the air atmosphere condition, carrying out cooling to obtain a light yellow product, carrying out heat preservation for 2-4h at the temperature of 160-180 ℃ after the light yellow product is mixed with thiourea, and carrying out cooling and grinding to obtain the product.
2. The method for catalytic oxidative degradation of aquaculture wastewater according to claim 1, wherein the mass ratio of tungsten hexacarbonyl to cesium nitrate to rubidium nitrate is 1: (0.5-0.8): (0.2-0.5); the mass ratio of the light yellow product to the thiourea is (1-3): 1.
3. the method for catalytic oxidative degradation of aquaculture wastewater according to claim 1, wherein the pH of the aquaculture wastewater is adjusted to 6-7; the constant temperature of the culture wastewater is 25-50 ℃.
4. The method for catalytic oxidative degradation of aquaculture wastewater according to claim 1, wherein the alkali metal-based tungsten bronze material has a grinding particle size of 0.1-100 μm and is added to the aquaculture wastewater in an amount of 10-100mg/L.
5. The method for catalytic oxidative degradation of aquaculture wastewater according to claim 1, wherein the illumination conditions are ultraviolet light, sunlight or xenon lamp illumination, and the light source has an optical power density of 50-300mW/cm 2 The distance between the light source and the liquid level of the cultivation wastewater is 10-50cm.
6. A method of catalytic oxidative degradation of aquaculture wastewater according to claim 1 wherein the contaminants comprise ammonia nitrogen and/or organic contaminants including antibiotics.
7. The method for catalytic oxidative degradation of aquaculture wastewater according to claim 6, wherein the concentration of ammonia nitrogen in the aquaculture wastewater is 0-200mg/L and the concentration of organic contaminants is 0-2000mg/L.
8. The method for catalytic oxidative degradation of aquaculture wastewater according to claim 1, wherein the photocatalyst further comprises a strengthening agent, and the preparation method of the strengthening agent comprises the following steps:
(1) Weighing triphenylamine and dissolving the triphenylamine in a dimethylformamide solvent, adding N-bromosuccinimide under ice water bath condition, fully stirring and mixing, preserving heat and reacting for 3-5 hours, concentrating under reduced pressure after the reaction is finished, washing the product with deionized water and saturated saline water respectively, removing unreacted reactants through a silica gel column to obtain a brominated product, dissolving the brominated product in the tetrahydrofuran solvent, adding butyl lithium solution under the conditions of protective atmosphere and ice water bath, preserving heat and stirring and reacting for 1-2 hours, adding isopropanol pinacol borate, continuing to preserving heat and stirring and reacting for 1-2 hours, stirring and reacting for 6-10 hours at normal temperature, adding cold deionized water after the reaction is finished, diluting a reaction system, concentrating after diethyl ether extraction, removing unreacted reactants through the silica gel column, and drying to obtain a precursor product;
(2) And (3) dissolving the precursor product in a toluene solvent under a protective atmosphere, adding 2, 3-bis (4-bromophenyl) -2-butenedinitrile and tetraethylammonium hydroxide, fully stirring and mixing, adding tribenzylidene acetone dipalladium and tris (o-methylphenyl) phosphorus, stirring and reacting for 24-36h under the protective atmosphere, cooling to room temperature after the reaction is finished, adding methanol to dilute a reaction system, separating and washing precipitate, and drying to obtain the strengthening agent.
9. The method for catalytic oxidative degradation of aquaculture wastewater according to claim 8, wherein the mass ratio of triphenylamine to N-bromosuccinimide in step (1) is 1: (1.4-1.5), the mass ratio of the bromination product to the isopropanol pinacol borate is 1: (1.4-1.5); the mass ratio of the precursor product to the 2, 3-bis (4-bromophenyl) -2-butenedinitrile, the tetraethylammonium hydroxide, the tribenzylideneacetone dipalladium, the tris (o-methylphenyl) phosphorus in step (2) is 1: (0.76-0.79): (0.25-0.27): (0.02-0.03): (0.05-0.08).
10. The method for catalytic oxidative degradation of aquaculture wastewater according to claim 8, wherein the mass ratio of the alkali metal-based tungsten bronze material to the strengthening agent is 1: (0.1-0.3).
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