CN107473387B - Constructed wetland dephosphorization matrix filler and preparation method thereof - Google Patents
Constructed wetland dephosphorization matrix filler and preparation method thereof Download PDFInfo
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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
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/32—Biological treatment of water, waste water, or sewage characterised by the animals or plants used, e.g. algae
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/105—Phosphorus compounds
Abstract
The invention discloses a phosphorus removal matrix filler for artificial wetlands and a preparation method thereof, which comprises the steps of firstly crushing wollastonite, fly ash and shale, sieving, washing, drying, uniformly mixing according to a ratio to obtain mixed powder, then grafting gamma-aminopropyltrimethoxysilane to the surface of the mixed powder to obtain a gamma-aminopropyltrimethoxysilane functionalized composite material, then polymerizing a methyl acrylate monomer to the surface of the gamma-aminopropyltrimethoxysilane functionalized composite material to obtain a polymethyl acrylate functionalized composite material, reacting the polymethyl acrylate functionalized composite material with diethylenetriamine to obtain an amino grafted composite material, and carrying out crosslinking reaction and granulation to obtain the phosphorus removal matrix filler. The filler obtained by the invention has the advantages of no toxicity, high strength, light weight, strong adsorption performance, good stability and the like, and has low production cost, strong pollutant removal capability and good phosphorus removal effect.
Description
Technical Field
The invention belongs to the technical field of environment function materials, and particularly relates to a constructed wetland dephosphorization matrix filler and a preparation method thereof.
Background
In recent years, with the progress of society, the living standard of human beings is improved, the discharge amount of pollutants is increased more and more, so that part of surface water bodies such as rivers and lakes and the like are eutrophicated, phosphorus is a limiting factor of lake eutrophication and is a factor which is preferably considered in the water body restoration process, once a large amount of phosphorus enters the water body, phytoplankton are often caused to grow rapidly, and further the safety of drinking water is influenced.
The phosphorus removal method mainly comprises a chemical precipitation method, a microbiological method, a physical adsorption method and the like. The chemical precipitation method mainly comprises a lime precipitation method, an iron salt precipitation method and an aluminum salt precipitation method. However, the three phosphorus removal methods have poor effect on removing low-concentration phosphorus-containing wastewater because the solubility product of calcium phosphate is large and the expected effect cannot be achieved by treating low-concentration phosphorus with lime; phosphorus with low concentration in water can form sol with iron and aluminum ions, the solubility is high, the phosphorus is not easy to separate from the water, and in order to achieve the phosphorus removal effect, the dosage of the medicament needs to be increased, so that the iron and aluminum metal ions have high residual quantity, and secondary pollution is easy to generate. Therefore, iron salts and aluminum salts cannot be directly used for the treatment of low-concentration phosphorus-containing wastewater. In addition, the chemical precipitation method can generate a large amount of chemical sludge, and if the chemical sludge is not properly treated, secondary pollution is easily caused, so that the application of the chemical sludge is limited; the phosphorus removal by the microbiological method is economic and has good removal effect, but because the growth of microorganisms has strict requirements on environmental temperature, pH value, nutrient elements, dissolved oxygen and the like, the stability is poor, and the dependency on the concentration of organic matters is strong, the concentration of the discharged phosphorus cannot reach the discharge standard under a plurality of conditions; the physical adsorption method utilizes functional materials to efficiently adsorb phosphorus, achieves the aim of removing phosphorus, mainly comprises zeolite molecular sieves, laterite and fly ash, and has the advantages of large capacity, low energy consumption, low pollution, quick removal, recyclability and the like, so that the physical adsorption method is widely applied to the aspect of phosphorus removal.
At present, the artificial wetland is often adopted to carry out advanced treatment on low-concentration phosphorus-containing wastewater, the artificial wetland is a novel ecological sewage treatment technology, and compared with the traditional sewage treatment method, the artificial wetland has the advantages of convenient maintenance and management, good treatment effect, low operation cost, high environmental aesthetic value and the like, and is widely applied to the field of treatment of urban domestic sewage and industrial and agricultural production wastewater. The removal of phosphorus in the sewage of the artificial wetland is mainly performed by filler adsorption, microbial adsorption and degradation and sludge precipitation, and the adsorption capacity depends on whether a medium filler has a high specific surface area and good hydraulic conductivity, so that the selection of an effective wetland matrix filler is very important for removing phosphorus in a water body.
The general artificial wetland substrate mainly comprises gravel, sandy soil, broken stones and the like, the substrate has poor phosphorus removal effect, other porous structure substrates such as calcite, hydrotalcite, coal gangue and the like, the calcite is used as phosphorus removal filler in the patent with the application number of CN201510178728.8, the hydrotalcite is used as phosphorus removal filler in the patent with the application number of CN201611004494.6, and the coal gangue is used for preparing phosphorus removal ceramsite in the patent with the application number of CN201610036142.2, so that the phosphorus adsorption removal effect is good, but the cost is high, and the popularization and the application are difficult. Therefore, the development of the novel efficient phosphorus removal wetland matrix filler has important practical significance for deeply removing phosphorus in sewage.
Disclosure of Invention
Based on the defects of the prior art, the invention aims to provide the constructed wetland dephosphorization matrix filler which has the advantages of no toxicity, high strength, light weight, strong adsorption performance, good stability and the like.
The invention also provides a preparation method of the artificial wetland dephosphorization matrix filler.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of constructed wetland dephosphorization matrix filler comprises the following steps:
(1) respectively crushing, sieving, washing and drying wollastonite, fly ash and shale to obtain wollastonite powder, fly ash powder and shale powder, and uniformly mixing the wollastonite powder, the fly ash powder and the shale powder according to the weight parts of (40-60) to (20-30) to (10-30) to obtain mixed powder;
(2) dispersing the mixed powder obtained in the step (1) in toluene, heating to 110-120 ℃ in a nitrogen atmosphere, adding gamma-aminopropyltrimethoxysilane, stirring for 10-12 hours, then carrying out solid-liquid separation, taking the solid, extracting and washing with ethanol, drying in vacuum, and grinding to obtain a gamma-aminopropyltrimethoxysilane functionalized composite material; wherein the mass ratio of the mixed powder to the gamma-aminopropyltrimethoxysilane is (1-2) to (0.6-1.1);
(3) dispersing the gamma-aminopropyl trimethoxy silane functional composite material obtained in the step (2) and methyl acrylate in water, heating to 55-65 ℃ in a nitrogen atmosphere, adding ammonium persulfate, stirring for 10-12 hours, then carrying out solid-liquid separation, extracting and washing solids with ethanol, and drying in vacuum to obtain a polymethyl acrylate functional composite material; wherein the mass ratio of the gamma-aminopropyltrimethoxysilane functionalized composite material to the methyl acrylate to the ammonium sulfate is (0.5-1) to (10-15) to (0.1-0.3);
(4) dispersing the polymethyl acrylate functionalized composite material obtained in the step (3) in acetone, adjusting the pH of the solution to 7-8 under the nitrogen atmosphere, adding diethylenetriamine, stirring at 90-98 ℃ for 6-8 hours, then carrying out solid-liquid separation, washing solids, and drying in vacuum to obtain an amino grafted composite material; wherein the mass ratio of the polymethyl acrylate functionalized composite material to the diethylenetriamine is 1: 14-20;
(5) adding the amino grafted composite material obtained in the step (4) into a polyvinyl alcohol aqueous solution, stirring and crosslinking for 4-6 hours, and granulating to obtain the amino grafted composite material; wherein the addition amount of the amino grafted composite material in the aqueous solution of the polyvinyl alcohol is 0.5-1 g/L.
Preferably, the aperture of the sieved mesh in the step (1) is 80-120 meshes, the washing in the step (1) adopts distilled water to shake and wash, and the drying in the step (1) is drying for 1.5-3 hours at 80-100 ℃.
Preferably, the vacuum drying in the step (2) and the vacuum drying in the step (3) are performed for 10 to 12 hours at a temperature of 60 to 90 ℃.
Preferably, the washing in the step (4) is washed to be neutral by distilled water, and the vacuum drying in the step (4) is carried out at the temperature of 50-70 ℃ for 12-24 hours.
Preferably, the mass percent of the polyvinyl alcohol in the aqueous solution of polyvinyl alcohol in the step (5) is 0.8-1.2%.
Preferably, the granulation in the step (5) is to prepare microspheres with the diameter of 3-4 mm in a granulator.
The artificial wetland dephosphorization matrix filler prepared by the method is adopted.
The wollastonite, the fly ash, the shale, the gamma-aminopropyl trimethoxy silane, the methyl acrylate and the diethylenetriamine are all common commercial products.
The preparation method of the artificial wetland dephosphorization matrix filler comprises the steps of firstly crushing wollastonite (Wo), Fly Ash (FA) and shale (Sh), sieving, washing, drying, uniformly mixing according to a ratio to obtain mixed powder, then grafting gamma-Aminopropyltrimethoxysilane (APTMS) to the surface of the mixed powder to obtain a gamma-aminopropyltrimethoxysilane functionalized composite material (WFS-APTMS), polymerizing a methyl acrylate monomer (Ma) to the surface of the WFS-APTMS to obtain a polymethyl acrylate functionalized composite material (WFS-APTMS-PMa), reacting the WFS-APTMS-PMa with Diethylenetriamine (DETA) to obtain an amino grafted composite material (WFS-APTMS-PMa-DETA), and granulating into high-strength functionalized microspheres after a crosslinking reaction. The reaction mechanism of the whole preparation process is as follows:
the invention has the beneficial effects that: the filler is prepared from inorganic materials commonly used in life, is suitable for ecological water treatment facilities such as artificial wetlands, biological filters and the like, has the advantages of no toxicity, high strength, light weight, strong adsorption performance, good stability and the like, is a carrier of microorganisms, and can efficiently adsorb phosphorus in wastewater. The invention has low production cost, strong pollutant removal capability and higher phosphorus removal effect than other common phosphorus removal fillers by more than 10 percent, and is beneficial to increasing the adsorption removal of phosphorus under the condition of the existence of organic matters in water.
Detailed Description
In order to make the technical purpose, technical solutions and advantages of the present invention clearer, the technical solutions of the present invention are further described with reference to specific examples, which are intended to explain the present invention and are not to be construed as limiting the present invention, and those who do not specify a specific technique or condition in the examples follow the techniques or conditions described in the literature in the art or follow the product specification.
Example 1
A preparation method of constructed wetland dephosphorization matrix filler comprises the following steps:
(1) respectively crushing wollastonite, fly ash and shale, sieving the wollastonite, the fly ash and the shale by a sieve of 100 meshes, then oscillating and washing the wollastonite, the fly ash and the shale in an oscillator for 1.5 hours by distilled water, and drying the wollastonite, the fly ash and the shale in a constant-temperature drying oven for 2 hours at 90 ℃ to obtain wollastonite powder, fly ash powder and shale powder; and mixing wollastonite powder, flyash powder and shale powder according to the weight ratio of 40: 30: 30, uniformly mixing to obtain mixed powder;
(2) adding 7.5g of the mixed powder obtained in the step (1) into a flask, adding 125mL of toluene, performing ultrasonic dispersion for 18 minutes, then placing the mixture into an oil bath pot, heating to 115 ℃ under the atmosphere of nitrogen, adding 4mL of gamma-aminopropyltrimethoxysilane, stirring at constant temperature for 11 hours, filtering, wrapping filter residues with filter paper, packaging with gauze, placing the gauze in an extraction device, using absolute ethyl alcohol as a detergent, placing glass beads to prevent explosive boiling, heating to boiling, extracting and washing for 11 hours, taking out the filter residues subjected to extraction washing, placing the filter residues in a vacuum drying oven, performing vacuum drying at 80 ℃ for 11 hours, and grinding into powder to obtain the gamma-aminopropyltrimethoxysilane functional composite material;
(3) adding 0.75g of the gamma-aminopropyltrimethoxysilane functionalized composite material obtained in the step (2) and 12.5g of methyl acrylate into a three-neck flask, adding 125mL of distilled water, performing ultrasonic dispersion for 18 minutes, then placing the mixture into a water bath kettle, heating to 60 ℃ under the atmosphere of nitrogen, adding 0.2g of ammonium persulfate, stirring for 11 hours, then filtering, taking the filter residue, wrapping the filter residue with filter paper, then placing the filter residue into an extraction device after gauze wrapping, using absolute ethyl alcohol as a detergent, placing glass beads to prevent explosion boiling, heating to boiling, extracting and washing for 11 hours, then taking out the filter residue after extraction and washing, placing the filter residue into a vacuum drying box, and performing vacuum drying at 80 ℃ for 11 hours to obtain the polymethyl acrylate functionalized composite material;
(4) adding 1g of the polymethyl acrylate functionalized composite material obtained in the step (3) into a three-neck flask, adding 22.5mL of acetone, ultrasonically dispersing for 18 minutes, adding 0.01g of NaOH under the nitrogen atmosphere, fully stirring for 3 minutes to adjust the pH value of the solution to 7-8, adding 17.5mL of diethylenetriamine, stirring for 7 hours under the condition of water bath at 95 ℃, filtering, washing filter residues with distilled water to be neutral, then placing in a vacuum drying oven, and vacuum drying for 18 hours at 60 ℃ to obtain an amino grafted composite material;
(5) adding the amino grafted composite material obtained in the step (4) into a polyvinyl alcohol aqueous solution, stirring and crosslinking for 5 hours, and then preparing microspheres with the diameter of 3-4 mm in a granulator to obtain a phosphorus removal matrix filler; wherein the mass percent of the polyvinyl alcohol in the aqueous solution of the polyvinyl alcohol is 1 percent, and the addition amount of the amino-grafted composite material in the aqueous solution of the polyvinyl alcohol is 0.75 g/L.
Performing column packing treatment on the prepared phosphorus removal substrate filler, wherein the diameter of the cross section of a column is 0.2m, the height of the filler is 1m, and the water flow speed is controlled to be 5 mL/min; adsorbing and removing the phosphorus-containing wastewater by using the prepared filler column, wherein the initial phosphorus concentration of the phosphorus-containing wastewater is 1.4mg/L, pH and is 4.0; under the condition of 25 ℃, after the phosphorus-containing wastewater is treated by a filler column, the phosphorus concentration of the effluent is 0.18mg/L, the effluent reaches the III-class standard of surface water environmental quality, and the removal rate is 87.1%.
Example 2
A preparation method of constructed wetland dephosphorization matrix filler comprises the following steps:
(1) respectively crushing wollastonite, fly ash and shale, sieving the wollastonite, the fly ash and the shale by a sieve of 80 meshes, then oscillating and washing the wollastonite, the fly ash and the shale in an oscillator for 1 hour by using distilled water, and drying the wollastonite, the fly ash and the shale in a constant-temperature drying oven at 80 ℃ for 2 hours to obtain wollastonite powder, fly ash powder and shale powder; and mixing the wollastonite powder, the fly ash powder and the shale powder according to the weight part of 50: 30: 20, uniformly mixing to obtain mixed powder;
(2) adding 5g of the mixed powder obtained in the step (1) into a flask, adding 100mL of toluene, performing ultrasonic dispersion for 15 minutes, then placing the mixed powder into an oil bath pot, heating to 110 ℃ under the atmosphere of nitrogen, adding 3mL of gamma-aminopropyltrimethoxysilane, stirring at constant temperature for 10 hours, filtering, wrapping filter residues with filter paper, then packaging with gauze, placing the filter residues into an extraction device, using absolute ethyl alcohol as a detergent, placing glass beads to prevent explosion boiling, heating to boiling, extracting and washing for 10 hours, then taking out the filter residues subjected to extraction washing, placing the filter residues into a vacuum drying oven, performing vacuum drying at 60 ℃ for 12 hours, and grinding into powder to obtain the gamma-aminopropyltrimethoxysilane functional composite material;
(3) adding 0.5g of the gamma-aminopropyl trimethoxy silane functionalized composite material obtained in the step (2) and 10g of methyl acrylate into a three-neck flask, adding 100mL of distilled water, performing ultrasonic dispersion for 15 minutes, then placing the mixture into a water bath kettle, heating to 55 ℃ under the atmosphere of nitrogen, adding 0.1g of ammonium persulfate, stirring for 10 hours, then filtering, wrapping filter residues with filter paper, then placing the wrapped filter residues into an extraction device after gauze packaging, using absolute ethyl alcohol as a detergent, placing glass beads to prevent explosion boiling, heating to boiling, extracting and washing for 10 hours, then taking out the filter residues subjected to extraction washing, placing the filter residues into a vacuum drying oven, and performing vacuum drying at 60 ℃ for 12 hours to obtain a polymethyl acrylate functionalized composite material;
(4) adding 1g of the polymethyl acrylate functionalized composite material obtained in the step (3) into a three-neck flask, adding 20mL of acetone, ultrasonically dispersing for 15 minutes, adjusting the pH value of the solution to 7-8 under the nitrogen atmosphere, adding 15mL of diethylenetriamine, stirring for 6 hours under the water bath condition of 90 ℃, filtering, washing filter residues to be neutral by using distilled water, then placing the filter residues into a vacuum drying oven, and carrying out vacuum drying for 24 hours at 50 ℃ to obtain an amino grafted composite material;
(5) adding the amino grafted composite material obtained in the step (4) into a polyvinyl alcohol aqueous solution, stirring and crosslinking for 4 hours, and then preparing microspheres with the diameter of 3-4 mm in a granulator to obtain a phosphorus removal matrix filler; wherein the mass percent of the polyvinyl alcohol in the aqueous solution of the polyvinyl alcohol is 0.8 percent, and the adding amount of the amino-grafted composite material in the aqueous solution of the polyvinyl alcohol is 0.5 g/L.
Performing column packing treatment on the prepared phosphorus removal substrate filler, wherein the diameter of the cross section of a column is 0.2m, the height of the filler is 1m, and the water flow speed is controlled to be 5 mL/min; adsorbing and removing the phosphorus-containing wastewater by using the prepared filler column, wherein the initial phosphorus concentration of the phosphorus-containing wastewater is 1.4mg/L, pH and is 4.0; under the condition of 25 ℃, after the phosphorus-containing wastewater is treated by a filler column, the phosphorus concentration of the effluent is 0.15mg/L, the effluent reaches the III-class standard of surface water environmental quality, and the removal rate is 89.3%.
Example 3
A preparation method of constructed wetland dephosphorization matrix filler comprises the following steps:
(1) respectively crushing wollastonite, fly ash and shale, sieving the wollastonite, the fly ash and the shale by a 120-mesh sieve, then oscillating and washing the wollastonite, the fly ash and the shale in an oscillator for 2 hours by using distilled water, and drying the wollastonite, the fly ash and the shale in a constant-temperature drying oven at 100 ℃ for 2 hours to obtain wollastonite powder, fly ash powder and shale powder; and mixing wollastonite powder, flyash powder and shale powder according to the weight portion of 60: 30: 10, uniformly mixing to obtain mixed powder;
(2) adding 10g of the mixed powder obtained in the step (1) into a flask, adding 150mL of toluene, performing ultrasonic dispersion for 20 minutes, then placing the mixed powder into an oil bath pot, heating to 120 ℃ under the atmosphere of nitrogen, adding 5mL of gamma-aminopropyltrimethoxysilane, stirring at constant temperature for 12 hours, filtering, wrapping filter residues with filter paper, then packaging with gauze, placing the filter residues into an extraction device, using absolute ethyl alcohol as a detergent, placing glass beads to prevent explosion boiling, heating to boiling, extracting and washing for 12 hours, then taking out the filter residues subjected to extraction washing, placing the filter residues into a vacuum drying oven, performing vacuum drying at 90 ℃ for 10 hours, and grinding into powder to obtain the gamma-aminopropyltrimethoxysilane functional composite material;
(3) adding 1g of the gamma-aminopropyltrimethoxysilane functionalized composite material obtained in the step (2) and 15g of methyl acrylate into a three-neck flask, then adding 150mL of distilled water, performing ultrasonic dispersion for 20 minutes, then placing the mixture into a water bath kettle, heating the mixture to 65 ℃ under the atmosphere of nitrogen, adding 0.3g of ammonium persulfate, stirring the mixture for 12 hours, then filtering the mixture, wrapping the filter residue with filter paper, then placing the wrapped filter residue into an extraction device after gauze packaging, using absolute ethyl alcohol as a detergent, placing glass beads to prevent explosion boiling, heating the wrapped filter residue to boiling, extracting and washing the wrapped filter residue for 12 hours, then taking out the filter residue after extraction and washing, placing the filter residue into a vacuum drying oven, and performing vacuum drying at 90 ℃ for 10 hours to obtain the polymethyl acrylate functionalized composite material;
(4) adding 1g of the polymethyl acrylate functionalized composite material obtained in the step (3) into a three-neck flask, adding 25mL of acetone, performing ultrasonic dispersion for 20 minutes, adjusting the pH value of the solution to 7-8 under the nitrogen atmosphere, adding 20mL of diethylenetriamine, stirring for 8 hours under the condition of a water bath at 98 ℃, filtering, washing filter residues to be neutral by using distilled water, then placing the filter residues into a vacuum drying oven, and performing vacuum drying for 12 hours at 70 ℃ to obtain an amino grafted composite material;
(5) adding the amino grafted composite material obtained in the step (4) into a polyvinyl alcohol aqueous solution, stirring and crosslinking for 6 hours, and then preparing microspheres with the diameter of 3-4 mm in a granulator to obtain a phosphorus removal matrix filler; wherein the mass percent of the polyvinyl alcohol in the aqueous solution of the polyvinyl alcohol is 1.2 percent, and the adding amount of the amino-grafted composite material in the aqueous solution of the polyvinyl alcohol is 1 g/L.
Performing column packing treatment on the prepared phosphorus removal substrate filler, wherein the diameter of the cross section of a column is 0.2m, the height of the filler is 1m, and the water flow speed is controlled to be 5 mL/min; adsorbing and removing the phosphorus-containing wastewater by using the prepared filler column, wherein the initial phosphorus concentration of the phosphorus-containing wastewater is 1.4mg/L, pH and is 4.0; under the condition of 25 ℃, after the phosphorus-containing wastewater is treated by a filler column, the phosphorus concentration of the effluent is 0.13mg/L, the effluent reaches the III-class standard of surface water environmental quality, and the removal rate is 90.7%.
Example 4
A preparation method of constructed wetland dephosphorization matrix filler comprises the following steps:
(1) respectively crushing wollastonite, fly ash and shale, sieving the wollastonite, the fly ash and the shale by a sieve of 100 meshes, then oscillating and washing the wollastonite, the fly ash and the shale in an oscillator for 1.5 hours by distilled water, and drying the wollastonite, the fly ash and the shale in a constant-temperature drying oven for 2 hours at 90 ℃ to obtain wollastonite powder, fly ash powder and shale powder; and mixing wollastonite powder, flyash powder and shale powder according to the weight portion of 60: 20: 10, uniformly mixing to obtain mixed powder;
(2) adding 7.5g of the mixed powder obtained in the step (1) into a flask, adding 125mL of toluene, performing ultrasonic dispersion for 18 minutes, then placing the mixture into an oil bath pot, heating to 115 ℃ under the atmosphere of nitrogen, adding 4mL of gamma-aminopropyltrimethoxysilane, stirring at constant temperature for 11 hours, filtering, wrapping filter residues with filter paper, packaging with gauze, placing the gauze in an extraction device, using absolute ethyl alcohol as a detergent, placing glass beads to prevent explosive boiling, heating to boiling, extracting and washing for 11 hours, taking out the filter residues subjected to extraction washing, placing the filter residues in a vacuum drying oven, performing vacuum drying at 80 ℃ for 11 hours, and grinding into powder to obtain the gamma-aminopropyltrimethoxysilane functional composite material;
(3) adding 0.75g of the gamma-aminopropyltrimethoxysilane functionalized composite material obtained in the step (2) and 12.5g of methyl acrylate into a three-neck flask, adding 125mL of distilled water, performing ultrasonic dispersion for 18 minutes, then placing the mixture into a water bath kettle, heating to 60 ℃ under the atmosphere of nitrogen, adding 0.2g of ammonium persulfate, stirring for 11 hours, then filtering, taking the filter residue, wrapping the filter residue with filter paper, then placing the filter residue into an extraction device after gauze wrapping, using absolute ethyl alcohol as a detergent, placing glass beads to prevent explosion boiling, heating to boiling, extracting and washing for 11 hours, then taking out the filter residue after extraction and washing, placing the filter residue into a vacuum drying box, and performing vacuum drying at 80 ℃ for 11 hours to obtain the polymethyl acrylate functionalized composite material;
(4) adding 1g of the polymethyl acrylate functionalized composite material obtained in the step (3) into a three-neck flask, adding 22.5mL of acetone, ultrasonically dispersing for 18 minutes, adding 0.01g of NaOH under the nitrogen atmosphere, fully stirring for 3 minutes to adjust the pH value of the solution to 7-8, adding 17.5mL of diethylenetriamine, stirring for 7 hours under the condition of water bath at 95 ℃, filtering, washing filter residues with distilled water to be neutral, then placing in a vacuum drying oven, and vacuum drying for 18 hours at 60 ℃ to obtain an amino grafted composite material;
(5) adding the amino grafted composite material obtained in the step (4) into a polyvinyl alcohol aqueous solution, stirring and crosslinking for 5 hours, and then preparing microspheres with the diameter of 3-4 mm in a granulator to obtain a phosphorus removal matrix filler; wherein the mass percent of the polyvinyl alcohol in the aqueous solution of the polyvinyl alcohol is 1 percent, and the addition amount of the amino-grafted composite material in the aqueous solution of the polyvinyl alcohol is 0.75 g/L.
Performing column packing treatment on the prepared phosphorus removal substrate filler, wherein the diameter of the cross section of a column is 1m, the height of the filler is 1m, and the water flow speed is controlled to be 5 mL/min; adsorbing and removing the phosphorus-containing wastewater by using the prepared filler column, wherein the initial phosphorus concentration of the phosphorus-containing wastewater is 1.4mg/L, pH and is 4.0; under the condition of 25 ℃, after the phosphorus-containing wastewater is treated by a filler column, the phosphorus concentration of the effluent is 0.25mg/L, the effluent reaches the IV-class standard of the environmental quality of surface water, and the removal efficiency is 82.1 percent.
Example 5
Preparing a phosphorus removal substrate filler according to the method of the embodiment 3, and carrying out column packing treatment on the phosphorus removal substrate filler, wherein the diameter of the cross section of a column is 0.5m, the height of the filler is 1m, and the water flow speed is controlled to be 5 mL/min; adsorbing and removing the phosphorus-containing wastewater by using the prepared filler column, wherein the initial phosphorus concentration of the phosphorus-containing wastewater is 1.4mg/L, pH and is 4.0; under the condition of 25 ℃, after the phosphorus-containing wastewater is treated by a filler column, the phosphorus concentration of the effluent is 0.23mg/L, the effluent reaches the IV-class standard of the environmental quality of surface water, and the removal efficiency is 83.6 percent.
Example 6
Preparing a dephosphorization matrix filler according to the method of the embodiment 3, and carrying out column packing treatment on the dephosphorization matrix filler, wherein the diameter of the cross section of a column is 0.2m, the height of the filler is 1m, and the water flow speed is controlled to be 15 mL/min; adsorbing and removing the phosphorus-containing wastewater by using the prepared filler column, wherein the initial phosphorus concentration of the phosphorus-containing wastewater is 1.4mg/L, pH and is 4.0; under the condition of 25 ℃, after the phosphorus-containing wastewater is treated by a filler column, the phosphorus concentration of the effluent is 0.3mg/L, the effluent reaches the IV-class standard of the environmental quality of surface water, and the removal efficiency is 78.6 percent.
Example 7
Preparing a phosphorus removal substrate filler according to the method of the embodiment 3, and carrying out column packing treatment on the phosphorus removal substrate filler, wherein the diameter of the cross section of a column is 0.2m, the height of the filler is 1m, and the water flow speed is controlled to be 25 mL/min; adsorbing and removing the phosphorus-containing wastewater by using the prepared filler column, wherein the initial phosphorus concentration of the phosphorus-containing wastewater is 1.4mg/L, pH and is 4.0; under the condition of 25 ℃, after the phosphorus-containing wastewater is treated by a packed column, the phosphorus concentration of the effluent is 0.32mg/L, the effluent reaches the IV-class standard of the environmental quality of surface water, and the removal efficiency is 77.1 percent.
Example 8
Preparing a phosphorus removal matrix filler according to the method of the embodiment 3, and carrying out column packing treatment on the phosphorus removal matrix filler, wherein the diameter of the cross section of a column is 0.2m, the height of the filler is 1m, and the water flow speed is controlled to be 5 mL/min; adsorbing and removing the phosphorus-containing wastewater by using the prepared filler column, wherein the initial phosphorus concentration of the phosphorus-containing wastewater is 1.4mg/L, pH and is 7.0; under the condition of 25 ℃, after the phosphorus-containing wastewater is treated by a filler column, the phosphorus concentration of the effluent is 0.26mg/L, the effluent reaches the IV-class standard of the environmental quality of surface water, and the removal efficiency is 81.4 percent.
Example 9
Preparing a phosphorus removal matrix filler according to the method of the embodiment 3, and carrying out column packing treatment on the phosphorus removal matrix filler, wherein the diameter of the cross section of a column is 0.2m, the height of the filler is 1m, and the water flow speed is controlled to be 5 mL/min; adsorbing and removing the phosphorus-containing wastewater by using the prepared filler column, wherein the initial phosphorus concentration of the phosphorus-containing wastewater is 1.4mg/L, pH and is 10.0; under the condition of 25 ℃, after the phosphorus-containing wastewater is treated by a filler column, the phosphorus concentration of the effluent is 0.33mg/L, the effluent reaches the IV-class standard of the environmental quality of surface water, and the removal efficiency is 76.4%.
Example 10
Preparing a phosphorus removal substrate filler according to the method of the embodiment 3, and carrying out column packing treatment on the phosphorus removal substrate filler, wherein the diameter of the cross section of a column is 0.5m, the height of the filler is 1m, and the water flow speed is controlled to be 5 mL/min; adsorbing and removing the phosphorus-containing wastewater by using the prepared filler column, wherein the initial phosphorus concentration of the phosphorus-containing wastewater is 1.4mg/L, pH and the COD is 50.2 mg/L; after the phosphorus-containing wastewater is treated by the filler column at 25 ℃, the phosphorus concentration of the effluent is 0.21mg/L, the COD of the effluent is 32.3mg/L, the effluent reaches the IV-class standard of the surface water environment quality, and the phosphorus removal efficiency is 85 percent.
Example 11
Preparing a phosphorus removal matrix filler according to the method of the embodiment 3, and carrying out column packing treatment on the phosphorus removal matrix filler, wherein the diameter of the cross section of a column is 0.2m, the height of the filler is 1m, and the water flow speed is controlled to be 5 mL/min; adsorbing and removing the phosphorus-containing wastewater by using the prepared filler column, wherein the initial phosphorus concentration of the phosphorus-containing wastewater is 1.4mg/L, pH and the COD is 60.1 mg/L; after the phosphorus-containing wastewater is treated by the filler column at 25 ℃, the phosphorus concentration of the effluent is 0.22mg/L, the COD of the effluent is 30.2mg/L, the effluent reaches the IV-class standard of the surface water environment quality, and the phosphorus removal efficiency is 84.3 percent.
Example 12
The phosphorus removal matrix filler is prepared according to the method of the embodiment 3 and applied to an artificial wetland, the type of the artificial wetland is a horizontal undercurrent type wetland, the area is 10m multiplied by 3m multiplied by 1m, wetland plants are selected from two of reed, calamus, cattail and arundo donax, the row spacing and the plant spacing are both 30cm, the wetland is arranged at the base of an ecological fine park of flourishing gardens group limited company, the inflow water of the artificial wetland system is the domestic sewage after biological treatment in the fine park, and the phosphorus concentration in the inflow water is 1.53mg/L, COD and is 65.5 mg/L; the domestic sewage is treated by the artificial wetland system, the concentration of phosphorus in the effluent is 0.2mg/L, the effluent is superior to the III-class standard of surface water environment quality, the phosphorus removal rate is 86.9 percent, and the COD of the effluent is 38.2 mg/L.
In conclusion, the phosphorus removal matrix filler prepared by the invention has good phosphorus removal effect, and is favorable for increasing the adsorption removal of phosphorus under the condition that organic matters exist in water.
The above embodiments are merely intended to illustrate the technical solution of the present invention and not to limit the same, and although the present invention has been described with reference to preferred embodiments thereof, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims.
Claims (6)
1. The preparation method of the artificial wetland dephosphorization matrix filler is characterized by comprising the following steps:
(1) respectively crushing, sieving, washing and drying wollastonite, fly ash and shale to obtain wollastonite powder, fly ash powder and shale powder, and uniformly mixing the wollastonite powder, the fly ash powder and the shale powder according to the weight parts of (40-60) to (20-30) to (10-30) to obtain mixed powder;
(2) dispersing the mixed powder obtained in the step (1) in toluene, heating to 110-120 ℃ in a nitrogen atmosphere, adding gamma-aminopropyltrimethoxysilane, stirring for 10-12 hours, then carrying out solid-liquid separation, taking the solid, extracting and washing with ethanol, drying in vacuum, and grinding to obtain a gamma-aminopropyltrimethoxysilane functionalized composite material; wherein the mass ratio of the mixed powder to the gamma-aminopropyltrimethoxysilane is (1-2) to (0.6-1.1);
(3) dispersing the gamma-aminopropyl trimethoxy silane functional composite material obtained in the step (2) and methyl acrylate in water, heating to 55-65 ℃ in a nitrogen atmosphere, adding ammonium persulfate, stirring for 10-12 hours, then carrying out solid-liquid separation, extracting and washing solids with ethanol, and drying in vacuum to obtain a polymethyl acrylate functional composite material; wherein the mass ratio of the gamma-aminopropyltrimethoxysilane functionalized composite material to the methyl acrylate to the ammonium sulfate is (0.5-1) to (10-15) to (0.1-0.3);
(4) dispersing the polymethyl acrylate functionalized composite material obtained in the step (3) in acetone, and adjusting the solution under the atmosphere of nitrogen
The pH value of the liquid is 7-8, then diethylenetriamine is added, the mixture is stirred for 6-8 hours at the temperature of 90-98 ℃, then solid-liquid separation is carried out, and the solid is washed and dried in vacuum to obtain the amino grafted composite material; wherein the mass ratio of the polymethyl acrylate functionalized composite material to the diethylenetriamine is 1: 14-20;
(5) adding the amino grafted composite material obtained in the step (4) into a polyvinyl alcohol aqueous solution, stirring and crosslinking for 4-6 hours,
granulating to obtain the product; wherein the addition amount of the amino grafted composite material in the aqueous solution of polyvinyl alcohol is 0.5-1 g/L;
the mass percentage of the polyvinyl alcohol in the aqueous solution of the polyvinyl alcohol in the step (5) is 0.8-1.2%.
2. The preparation method of the artificial wetland dephosphorization matrix filler according to claim 1, characterized in that: the size of the sieved mesh in the step (1) is 80-120 meshes, the washing in the step (1) is vibration washing by using distilled water, and the drying in the step (1) is drying for 1.5-3 hours at the temperature of 80-100 ℃.
3. The preparation method of the artificial wetland dephosphorization matrix filler according to claim 1, characterized in that: and (3) vacuum drying at 60-90 ℃ for 10-12 hours.
4. The preparation method of the artificial wetland dephosphorization matrix filler according to claim 1, characterized in that: and (4) washing by using distilled water until the washing is neutral, wherein the vacuum drying temperature in the step (4) is 50-70 ℃, and the time is 12-24 hours.
5. The preparation method of the artificial wetland dephosphorization matrix filler according to claim 1, characterized in that: and (5) granulating to prepare microspheres with the diameter of 3-4 mm in a granulator.
6. The artificial wetland dephosphorization matrix filler prepared by the method of any one of claims 1 to 5.
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| CN1587103A (en) * | 2004-09-02 | 2005-03-02 | 上海交通大学 | Filter material having phosphor adsorbing and biological membrane function and its preparing method |
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| US8252182B1 (en) * | 2008-09-11 | 2012-08-28 | University Of Central Florida Research Foundation, Inc. | Subsurface upflow wetland system for nutrient and pathogen removal in wastewater treatment systems |
| CN102746023A (en) * | 2012-06-15 | 2012-10-24 | 中国建筑股份有限公司 | Constructed wetland matrix filling material for simultaneous nitrogen and phosphorus removal and its preparation method |
| CN104437382A (en) * | 2014-10-15 | 2015-03-25 | 中国科学院生态环境研究中心 | Antibiotic and heavy metal removed meso-porous silicon based bifunctional adsorbing material as well as preparation method and application thereof |
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| CN1587103A (en) * | 2004-09-02 | 2005-03-02 | 上海交通大学 | Filter material having phosphor adsorbing and biological membrane function and its preparing method |
| US8252182B1 (en) * | 2008-09-11 | 2012-08-28 | University Of Central Florida Research Foundation, Inc. | Subsurface upflow wetland system for nutrient and pathogen removal in wastewater treatment systems |
| CN102247807A (en) * | 2011-05-17 | 2011-11-23 | 江苏麦阁吸附剂有限公司 | Preparation method and usage of modified attapulgite adsorption material |
| CN102746023A (en) * | 2012-06-15 | 2012-10-24 | 中国建筑股份有限公司 | Constructed wetland matrix filling material for simultaneous nitrogen and phosphorus removal and its preparation method |
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