CN114956278A - Modified plant tannin environment-friendly magnetic flocculant and method for treating high algae water body step by step - Google Patents
Modified plant tannin environment-friendly magnetic flocculant and method for treating high algae water body step by step Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 26
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- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 25
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- 231100000765 toxin Toxicity 0.000 claims abstract description 21
- 108700012359 toxins Proteins 0.000 claims abstract description 21
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 claims abstract description 20
- 239000000178 monomer Substances 0.000 claims abstract description 15
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 7
- 239000011259 mixed solution Substances 0.000 claims description 27
- 239000003999 initiator Substances 0.000 claims description 24
- 238000002360 preparation method Methods 0.000 claims description 23
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 21
- 239000012498 ultrapure water Substances 0.000 claims description 21
- 241000192700 Cyanobacteria Species 0.000 claims description 20
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 claims description 20
- 239000007864 aqueous solution Substances 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 16
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
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- 238000011068 loading method Methods 0.000 description 1
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- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
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- HNONEKILPDHFOL-UHFFFAOYSA-M tolonium chloride Chemical compound [Cl-].C1=C(C)C(N)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 HNONEKILPDHFOL-UHFFFAOYSA-M 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
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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
- C02F1/48—Treatment of water, waste water, or sewage with magnetic or electric fields
- C02F1/488—Treatment of water, waste water, or sewage with magnetic or electric fields for separation of magnetic materials, e.g. magnetic flocculation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- 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
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
-
- 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
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The invention provides a modified plant tannin environment-friendly magnetic flocculant and a method for treating a high algae water body step by step, which are characterized in that the surface of ferroferric oxide nano particles is coated with copolymerization tannin and polyethyleneimine to obtain the modified plant tannin environment-friendly magnetic flocculant, wherein the copolymerization tannin is a product of copolymerization of tannin with acrylamide and methacryloyloxyethyl trimethyl ammonium chloride monomers. The method comprises the steps of treating blue algae cells by using permonosulfate with mild oxidizability, reducing the stability of the blue algae cells by changing the surface properties of the blue algae cells, then rapidly separating and recovering blue algae by using the magnetic flocculant, and finally introducing ultraviolet equipment to rapidly activate the permonosulfate so as to completely degrade algae organic matters and algal toxins. The magnetic flocculant provided by the invention can be used for easily capturing algae cells, is small in dosage, and can be used for treating a high algae water body step by step, so that the algae cells can be efficiently removed, and algae organic matters and algae toxins can be rapidly and thoroughly degraded.
Description
Technical Field
The invention relates to the technical field of high algae water body treatment, in particular to a modified plant tannin environment-friendly magnetic flocculant and a method for treating a high algae water body step by step.
Background
Due to the advantages of high efficiency, time saving, simple operation, low energy consumption and the like, the magnetic flocculation technology based on the magnetic particles is widely applied to the field of water treatment such as high algae water body and the like. The surface of the cyanobacteria cell is usually electronegative, and Fe 3 O 4 The isoelectric point of the particles is about pH3.0-5.0, which makes it difficult to meet the treatment requirements of high algae water (usually pH 7.0-9.3). Therefore, the improvement of the isoelectric point and the surface positive charge quantity of the magnetic particles is the key for the popularization and the application of the magnetic flocculation technology.
Generally, a cationic polymer is coated on the surface of magnetic particles to increase the isoelectric point and the surface positive charge of the magnetic particles, and artificially synthesized polymers, such as Polyacrylamide (PAM) and polyaluminum chloride (PAC), have been widely used for coating of magnetic particles. However, residual acrylamide monomer and aluminum ion are toxic, which causes secondary pollution of natural water.
Plant tannin is a biomass resource which is abundant in reserves and easy to obtain, and is a fourth forest byproduct second to cellulose, lignin and hemicellulose. Naturally extracted plant tannin has a low isoelectric point (pHpzc is 2.0-3.0), and the plant tannin generally needs to be modified by cationization to be used as a cation coating material. The existing plant tannin cation coating materials are mainly obtained by ammonium modification, but have the problems of low charge density, large dosage and the like, so that the development of novel plant tannin cation coating materials is urgently needed.
In addition, although the magnetic flocculation technique has a good effect of removing algae cells, the removal efficiency of the magnetic flocculation technique on organic matters in algae is very limited. Research shows that the removal rate of the organic matters of the algae after being treated by the magnetic flocculant is only about 10-30%. Meanwhile, many researches show that the removal rate of the algal toxin by the magnetic flocculation is lower than 50%. Therefore, a technology for synchronously realizing the efficient removal of algae cells and the effective control of algae organic matters is needed.
Disclosure of Invention
The invention aims to provide a modified plant tannin environment-friendly magnetic flocculant and a method for treating a high-algae water body step by step aiming at the defects of the prior art.
According to the first aspect of the invention, the modified plant tannin environment-friendly magnetic flocculant comprises ferroferric oxide nanoparticles, wherein the surfaces of the ferroferric oxide nanoparticles are coated with copolymerized tannin and polyethyleneimine, and the copolymerized tannin is a product obtained by copolymerizing tannin with acrylamide and methacryloyloxyethyl trimethyl ammonium chloride monomers.
Preferably, the particle size of the ferroferric oxide nano particles is 50-200 nm.
According to the second aspect of the invention, the preparation method of the modified plant tannin environment-friendly magnetic flocculant is provided, and comprises the following steps:
preparation of copolymerized tannin: dispersing tannin extract in ultrapure water, adding an initiator, and fully activating tannin by the initiator to obtain a first mixed solution;
dropwise adding a mixed aqueous solution of an acrylamide monomer and a methacryloyloxyethyl trimethyl ammonium chloride monomer into the first mixed solution to obtain a second mixed solution, reacting the second mixed solution under the conditions of stirring and water bath, and purifying, cleaning and drying a product obtained after the reaction is finished to obtain a copolymerized tannin TAD;
the preparation method of the modified plant tannin environment-friendly magnetic flocculant comprises the following steps: dissolving TAD and polyethyleneimine in ultrapure water dispersed with ferroferric oxide nanoparticles to obtain a third mixed solution, adding glutaraldehyde into the third mixed solution, carrying out oscillation reaction under the condition of constant-temperature water bath, separating a product obtained after the reaction is finished, washing and drying to obtain the modified plant tannin environment-friendly magnetic flocculant.
Preferably, in the first mixed solution, the concentration of the initiator is 0.01-0.02 mol/L, the mass ratio of the initiator to the tannin extract is (1-1.5): 5, and the initiation is carried outThe agent is Ce (NH) 4 ) 2 (NO 3 ) 6 An aqueous solution.
Preferably, in the second mixed solution, the mass ratio of the acrylamide monomer to the tannin extract is (1-3): 1, and the mass ratio of the acrylamide monomer to the methacryloyloxyethyl trimethyl ammonium chloride monomer is (1-5).
Preferably, in the third mixed solution, the mass ratio of the ferroferric oxide nanoparticles to the TAD is 1 (5-10), and the molar ratio of the TAD to the polyethyleneimine is 3-5: 1;
the mass ratio of the volume of the glutaraldehyde to the TAD is (5-10) mL (1.0-2.0) g, and the purity of the glutaraldehyde is 50 wt.%.
According to a third aspect of the invention, the application of the modified plant tannin environment-friendly magnetic flocculant in treating high algae water is provided.
According to the fourth aspect of the invention, the method for stepwise treating the high algae water body by adopting the modified plant tannin environment-friendly magnetic flocculant comprises the following steps:
s1, adding monosulfate into the high algae water body, and fully mixing to obtain a first water body;
s2, putting the magnetic flocculating agent into the first water body obtained in the step S1, fully mixing, and then carrying out magnetic separation to separate the cyanobacteria cells in the first water body, so as to obtain a cyanobacteria cell-removed cyanobacteria liquid, namely a second water body;
s3, adding peroxymonosulfate into the second water body obtained in the step S2, reacting under the condition of ultraviolet irradiation, and degrading algae organic matters and algal toxins;
wherein the magnetic flocculant is the modified plant tannin environment-friendly magnetic flocculant.
Preferably, in the step S1, the amount of the permonosulfate is determined according to the density of algae in the water body, and the density of the algae is 1.11 to 8.87 × 10 6 The dosage of the peroxymonosulfate is 100-200mg/L for each cell/mL.
Preferably, in the step S2, the amount of the magnetic flocculant is determined according to the density of algae in the water body, and the density of algae is 0.11-9.87 × 10 6 When the cell is per mL, the dosage of the magnetic flocculant is 10-200 mg/L.
Preferably, in the step S3, the adding concentration range of the peroxymonosulfate is 400-600 mg/L.
Preferably, in step S3, the ultraviolet irradiation conditions are as follows:
the ultraviolet wavelength range is 200-245nm, and the ultraviolet irradiation intensity>1.15mW/cm 2 The ultraviolet irradiation time range is 3-4 h.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the modified plant tannin environment-friendly magnetic flocculant, copolymerization tannin and polyethyleneimine cationic polymer are grafted on the surface of nano ferroferric oxide, and the isoelectric point is increased to be more than pH12.0, so that the flocculant can capture electronegative algae cells more easily; in addition, the cationic degree of the coated ferroferric oxide is as high as 1.2-2.3, so that the dosage of the magnetic flocculant is greatly reduced, and the sludge yield and the treatment cost are reduced.
2. The method for treating the high algae water body step by step firstly utilizes the oxidant to change the surface characteristics of algae cells, reduce the surface charges of the algae cells and destroy the stability of algae liquid, thereby providing an environment for the magnetic flocculant to effectively capture the blue algae cells; then removing algae cells on the electronegative surface by a magnetic flocculant with high cationic degree through an electric neutralization effect, promoting the magnetic flocculant to capture the algae cells through a bridging effect by a copolymerization tannin and a polyethyleneimine-extended molecular chain and rich active sites, thereby flocculating algae in a water body, and after flocculation and coagulation, rapidly separating and recovering magnetic algae mud under the assistance of an external magnetic field; when the algal cells are isolated, the introduced UV rapidly activates the peroxymonosulfate, producing large amounts of active free radicals such as SO 4 ·- 、 · OH and 1 O 2 and the algae toxins and other algae organic matters are rapidly degraded through the free radicals, so that the rapid mineralization of the algae liquid is realized.
3. In the method for treating the high algae water body, the integrity of algae cells cannot be damaged in the whole process, so that the release of intracellular organic matters such as algal toxins cannot be caused, a stable environment is provided for the whole degradation removal process, secondary pollution is avoided, the degradation removal efficiency is improved, the process is simple, the operation is easy, the coupling with the existing process is strong, and the method has a large-scale application prospect.
Drawings
FIG. 1 is a synthetic mechanism diagram of the modified plant tannin environment-friendly magnetic flocculant.
Fig. 2(a) is an SEM image of acacia mearnsii tannin in example 1 of the present invention.
Fig. 2(b) is an enlarged view of a circled portion in fig. 2 (a).
FIG. 2(c) is an SEM photograph of a copolymerized tannin in example 1 of the present invention.
Fig. 2(d) is an enlarged view of a circled portion in fig. 2 (c).
Fig. 3(a) is an SEM image of the ferroferric oxide nanoparticles in example 1 of the present invention.
Fig. 3(b) is an enlarged view of a circled portion in fig. 3 (a).
FIG. 3(c) is TP @ Fe in example 1 of the present invention 3 O 4 SEM image of (d).
Fig. 3(d) is an enlarged view of a circled portion in fig. 3 (c).
FIGS. 3(e), 3(f) and 3(g) are respectively TP @ Fe in example 1 of the present invention 3 O 4 EDX-mapping of Fe, N and O.
FIGS. 3(h) and 3(i) are TP @ Fe in example 1 of the present invention 3 O 4 A TEM image of (a).
FIG. 4 is an FTIR chart of the modified plant tannin environment-friendly magnetic flocculant of the example 1 of the invention.
FIG. 5 is an XPS diagram of a modified plant tannin environment-friendly magnetic flocculant in example 1 of the invention.
FIG. 6 is a VSM diagram of the modified plant tannin environment-friendly magnetic flocculant in example 1 of the invention.
Detailed Description
In order to better understand the technical content of the present invention, specific embodiments are described below with reference to the accompanying drawings.
In this disclosure, aspects of the present invention are described with reference to the accompanying drawings, in which a number of illustrative embodiments are shown. Embodiments of the present disclosure are not necessarily intended to include all aspects of the invention. It should be appreciated that the various concepts and embodiments described above, as well as those described in greater detail below, may be implemented in any of numerous ways.
With reference to fig. 1-6, in order to solve the problem of low removal rate of algae organic matters and algae toxins when treating a high algae water body, the invention provides a modified plant tannin environment-friendly magnetic flocculant and a method for treating the high algae water body step by step.
In an exemplary embodiment of the invention, a modified plant tannin environment-friendly magnetic flocculant is provided, and comprises ferroferric oxide nanoparticles, wherein the surfaces of the ferroferric oxide nanoparticles are coated with copolymerized tannin and polyethyleneimine, and the copolymerized tannin is a product of copolymerization of tannin and acrylamide and methacryloyloxyethyl trimethyl ammonium chloride monomers.
In a preferred embodiment, the particle size of the ferroferric oxide nano particles is 50-200 nm.
In another exemplary embodiment of the invention, a preparation method of the modified plant tannin environment-friendly magnetic flocculant is provided, which comprises the following steps:
preparation of copolymerized tannin: dispersing Tannin extract (Tannin) in ultrapure water, adding an initiator, and fully activating Tannin by the initiator to obtain a first mixed solution;
dropwise adding a mixed aqueous solution of an Acrylamide Monomer (AM) and a methacryloyloxyethyl trimethyl ammonium chloride monomer (DMC) into the first mixed solution to obtain a second mixed solution, reacting the second mixed solution under the conditions of stirring and water bath, and purifying, cleaning and drying a product obtained after the reaction is finished to obtain a copolymerized tannin TAD;
the preparation method of the modified plant tannin environment-friendly magnetic flocculant comprises the following steps: dissolving TAD and Polyethyleneimine (PEI) in ultrapure water dispersed with ferroferric oxide nanoparticles to obtain a third mixed solution, adding glutaraldehyde into the third mixed solution, and placing in a constant-temperature water bathOscillating to react under the condition, separating a product obtained after the reaction is finished, washing and drying to obtain the modified plant tannin environment-friendly magnetic flocculant TP @ Fe 3 O 4 。
In a preferred embodiment, the concentration of the initiator in the first mixed solution is 0.01-0.02 mol/L, the mass ratio of the initiator to the tannin extract is (1-1.5): 5, and the initiator is Ce (NH) 4 ) 2 (NO 3 ) 6 An aqueous solution.
In a preferred embodiment, in the second mixed solution, the mass ratio of the acrylamide monomer to the tannin extract is (1-3): 1, and the mass ratio of the acrylamide monomer to the methacryloyloxyethyl trimethyl ammonium chloride monomer is (1-5).
In a preferred embodiment, in the third mixed solution, the mass ratio of the ferroferric oxide nanoparticles to the TAD is 1 (5-10), and the molar ratio of the TAD to the polyethyleneimine is (3-5): 1;
the mass ratio of the volume of the glutaraldehyde to the TAD is (5-10) mL (1.0-2.0) g, and the purity of the glutaraldehyde is 50 wt.%.
In another exemplary embodiment of the invention, the application of the modified plant tannin environment-friendly magnetic flocculant in treating high algae water is provided.
In another exemplary embodiment of the invention, a method for stepwise treating a high algae water body by using the modified plant tannin environment-friendly magnetic flocculant is provided, which comprises the following steps:
s1, adding monosulfate into the high algae water body, and fully mixing to obtain a first water body;
s2, putting the magnetic flocculating agent into the first water body obtained in the step S1, fully mixing, and then carrying out magnetic separation to separate the cyanobacteria cells in the first water body, so as to obtain a cyanobacteria cell-removed cyanobacteria liquid, namely a second water body;
s3, adding peroxymonosulfate into the second water body obtained in the step S2, reacting under the condition of ultraviolet irradiation, and degrading algae organic matters and algal toxins;
wherein the magnetic flocculant is the modified plant tannin environment-friendly magnetic flocculant.
In a preferred embodiment, in step S1, the amount of the permonosulfate is determined according to the density of algae in the water body, and the density of the algae is 1.11-8.87 × 10 6 The dosage of the peroxymonosulfate is 100-200mg/L for each cell/mL.
In a preferred embodiment, in step S2, the amount of the magnetic flocculant is determined according to the density of algae in the water body, and the density of algae is 0.11 to 9.87 × 10 6 When each cell/mL is detected, the dosage of the magnetic flocculant is 10-200 mg/L.
In a preferred embodiment, in the step S3, the adding concentration of the peroxymonosulfate is in the range of 400-600 mg/L.
In a preferred embodiment, in step S3, the ultraviolet irradiation conditions are as follows:
the ultraviolet wavelength range is 200-245nm, and the ultraviolet irradiation intensity>1.15mW/cm 2 The ultraviolet irradiation time range is 3-4 h.
For better understanding, the present invention is further described below with reference to several specific examples, but the process is not limited thereto and the present disclosure is not limited thereto.
Preparation of modified plant tannin environment-friendly magnetic flocculant
[ example 1 ]
Preparation of the copolymerized tannin TAD: firstly, 5g tannin extract is dispersed in 150mL water, continuously stirred for 30min, and then 1.09g Ce (NH) of initiator is rapidly added 4 ) 2 (NO 3 ) 6 An aqueous solution. The system is maintained for 10min, and the initiator fully activates the tannin.
Then, a mixed aqueous solution of Acrylamide (AM) and methacryloyloxyethyl trimethyl ammonium chloride (DMC) monomers was added dropwise to the reactor while continuously stirring. The product was heated in a water bath at 50 ℃. The product is purified and washed by acetone/ether and dried in vacuum at 50 ℃ to obtain TAD.
Modified plant tannin environment-friendly magnetic flocculant TP @ Fe 3 O 4 The preparation of (1): 0.2g of Fe 3 O 4 The nanoparticles were added to a conical flask filled with 150mL of ultrapure water and sonicated for 10 minutes. Subsequently, 1.5g TAD and 0.5g polyethyleneimine were thoroughly mixedDissolved in 20mL of ultrapure water in which ferroferric oxide nanoparticles are dispersed. Then, 5.0mL of glutaraldehyde (50 wt%) was added to the mixture while shaking the sealed flask in a 25 ℃ thermostatic waterbath shaker at 200 rpm. The product was then isolated using a magnet and repeatedly rinsed with ultra pure water. The washed sample is dried in an oven below 60 ℃ to constant weight.
[ example 2 ]
Preparation of copolymerized tannin: firstly 2g tannin extract is dispersed in 150mL water, continuously stirred for 30min, then 0.0822g initiator Ce (NH) is rapidly added 4 ) 2 (NO 3 ) 6 The final concentration of the aqueous solution was 0.01 mol/L. The system is maintained for 10min, and the initiator fully activates the tannin.
Then, a mixed aqueous solution of 6g of Acrylamide (AM) and 6g of methacryloyloxyethyl trimethyl ammonium chloride (DMC) monomer was dropwise added to the reactor while continuously stirring. The product was heated in a water bath at 50 ℃. The product is purified and washed by acetone/ether and dried in vacuum at 50 ℃ to obtain TAD.
The preparation method of the modified plant tannin environment-friendly magnetic flocculant comprises the following steps: 0.2g of Fe 3 O 4 The nanoparticles were added to a conical flask filled with 150mL of ultrapure water and sonicated for 10 minutes. Subsequently, 1.0g of TAD and 0.2g of polyethyleneimine were sufficiently dissolved in 20mL of ultrapure water in which ferroferric oxide nanoparticles were dispersed. Then, 10.0mL of glutaraldehyde (50 wt%) was added to the mixture while shaking the sealed flask in a 25 ℃ thermostatic water bath shaker at 200 rpm. The product was then isolated using a magnet and repeatedly rinsed with ultra pure water. The washed sample is dried in an oven below 60 ℃ to constant weight.
[ example 3 ]
Preparation of copolymerized tannin: firstly 3g tannin extract is dispersed in 150mL water, continuously stirred for 30min, then 1.233g initiator Ce (NH) is rapidly added 4 ) 2 (NO 3 ) 6 The final concentration of the aqueous solution was 0.015 mol/L. The system is maintained for 10min, and the initiator fully activates the tannin.
Then, a mixed aqueous solution of 4.5g of Acrylamide (AM) and 13.5g of methacryloyloxyethyl trimethylammonium chloride (DMC) monomer was dropwise added to the reactor while continuously stirring. The product was heated in a water bath at 50 ℃. The product is purified and washed by acetone/ether and dried in vacuum at 50 ℃ to obtain TAD.
The preparation method of the modified plant tannin environment-friendly magnetic flocculant comprises the following steps: 0.3g of Fe 3 O 4 The nanoparticles were added to a conical flask filled with 150mL of ultrapure water and sonicated for 10 minutes. Subsequently, 2.25g of TAD and 0.75g of polyethyleneimine were sufficiently dissolved in 20mL of ultrapure water in which ferroferric oxide nanoparticles were dispersed. Then, 7.5mL of glutaraldehyde (50 wt%) was added to the mixture while shaking the sealed flask in a 25 ℃ thermostatic waterbath shaker at 200 rpm. The product was then isolated using a magnet and repeatedly rinsed with ultra pure water. The washed sample is dried in an oven below 60 ℃ to constant weight.
[ example 4 ]
Preparation of copolymerized tannin: firstly, 5g tannin extract is dispersed in 150mL water, continuously stirred for 30min, and then 1.233g initiator Ce (NH) is rapidly added 4 ) 2 (NO 3 ) 6 The final concentration of the aqueous solution was 0.015 mol/L. The system is maintained for 10min, and the initiator fully activates the tannin.
Then, a mixed aqueous solution of 7.5g of Acrylamide (AM) and 18.75g of methacryloyloxyethyl trimethylammonium chloride (DMC) monomer was dropwise added to the reactor while continuously stirring. The product was heated in a water bath at 50 ℃. The product is purified and washed by acetone/ether and dried in vacuum at 50 ℃ to obtain TAD.
The preparation method of the modified plant tannin environment-friendly magnetic flocculant comprises the following steps: 0.4g of Fe 3 O 4 The nanoparticles were added to a conical flask filled with 150mL of ultrapure water and sonicated for 10 minutes. Subsequently, 2.0g of TAD and 0.4g of polyethyleneimine were sufficiently dissolved in 20mL of ultrapure water in which ferroferric oxide nanoparticles were dispersed. Then, 5mL of glutaraldehyde (50 wt%) was added to the mixture while shaking the sealed flask in a 25 ℃ thermostatic water bath shaker at 200 rpm. The product was then isolated using a magnet and repeatedly rinsed with ultra pure water. The washed sample is dried in an oven below 60 ℃ to constant weight.
[ example 5 ]
Preparation of copolymerized tannin: firstly 3g tannin extract is dispersed in 150mL water, continuously stirred for 30min, then 1.644g initiator Ce (NH) is rapidly added 4 ) 2 (NO 3 ) 6 The final concentration of the aqueous solution was 0.02 mol/L. The system is maintained for 10min, and the initiator fully activates the tannin.
Then, a mixed aqueous solution of 9g of Acrylamide (AM) and 9g of methacryloyloxyethyl trimethyl ammonium chloride (DMC) monomer was dropwise added to the reactor while continuously stirring. The product was heated in a water bath at 50 ℃. The product is purified and washed by acetone/ether and dried in vacuum at 50 ℃ to obtain TAD.
The preparation method of the modified plant tannin environment-friendly magnetic flocculant comprises the following steps: 0.2g of Fe 3 O 4 The nanoparticles were added to a conical flask filled with 150mL of ultrapure water and sonicated for 10 minutes. Subsequently, 1.5g of TAD and 0.3g of polyethyleneimine were sufficiently dissolved in 7.5mL of ultrapure water in which ferroferric oxide nanoparticles were dispersed. Then, 7.5mL of glutaraldehyde (50 wt%) was added to the mixture while shaking the sealed flask in a thermostatic water bath shaker at 25 ℃ at a rotation speed of 200 rpm. The product was then isolated using a magnet and repeatedly rinsed with ultra pure water. The washed sample is dried in an oven below 60 ℃ to constant weight.
Testing
[ example 6 ]
3 4 Cationic degree test of TP @ FeO obtained in examples 1 to 5
10mL of the magnetic flocculant solution was pipetted into a 100mL conical flask, a drop of toluidine blue indicator was added, and the solution was titrated with a standard solution of potassium polyvinyl sulfate until the color changed from blue to light purple. During the titration process, the liquid to be titrated turns turbid from clear to clear, and when the titration end point is approached, the turbid turns to clear, and precipitates appear. Calculating the charge density C of the magnetic flocculant solution according to the following formula 2 。
In the formula, C 1 Charge density of the potassium polyvinyl sulfate standard solution, mol/L
C 2 Charge density of the magnetic flocculant solution, mol/L
V-titration of the volume of the magnetic flocculant solution depleted in the potassium polyvinyl sulfate solution, mL
V 0 Titration of the blank to consume volume of potassium polyvinyl sulfate solution, mL
And m-10mL of the mass of the magnetic flocculant in the sample to be detected.
Calculated to obtain the magnetic flocculant TP @ Fe 3 O 4 The cationic degree of (A) is 1.2 to 2.3.
[ example 7 ]
SEM and TEM
SEM and TEM tests were performed on the sample obtained in example 1, and the results are shown in FIGS. 2 to 3.
According to the SEM image, compared with the black wattle tannin (fig. 2(a) and 2(b)), the TAD (fig. 2(c) and 2(d)) is in a dense cluster shape, the surface is uneven, the holes are numerous, and the abundant pore structure is very favorable for the combination of the black wattle tannin and pollutants.
And Fe 3 O 4 Has a spherical structure (FIGS. 3(a) and 3(b)), and Fe 3 O 4 After TAD and PEI coating, it was observed from both SEM (FIGS. 3(c), 3(d)) and TEM (FIGS. 3(h), 3(i)) that the polymer analog was tightly attached to the surface of Fe3O4 particles, Fe 3 O 4 The particles are almost encapsulated throughout the material matrix.
The EDX-mapping plots show (fig. 3(e), 3(f), 3(g)), N, O, Fe and the elements are uniformly distributed in the material matrix.
From the above, TAD and PEI can be proved to be coated on Fe successfully 3 O 4 A surface.
[ example 7 ]
FTIR testing
The infrared test was performed on the sample obtained in example 1, and the results are shown in fig. 4.
From the figure, TP @ Fe can be seen 3 O 4 In FTIR spectrum of (5) at 570cm -1 A peak appears, which is in contrast to Fe 3 O 4 Fe-O (587 cm) -1 ) Vibration related, indicating Fe 3 O 4 Is successfully loaded.
At TP @ Fe 3 O 4 In the spectrum of 1632, 1384 and 956cm -1 And a plurality of peaks, which are consistent with the peaks in the spectra of TAD and PEI, further demonstrate the successful loading of TAD and PEI.
Therefore, the invention can further prove that the modified plant tannin environment-friendly magnetic flocculant TP @ Fe is successfully prepared 3 O 4 。
[ example 8 ]
XPS test
The XPS test was performed on the sample obtained in example 1, and the result is shown in fig. 5.
It can be seen from the figure that the Fe is compared with the Fe 3 O 4 At TP @ Fe 3 O 4 The peaks associated with N1s are clearly visible, and the TAD and PEI contain abundant nitrogen-containing functional groups, which indicates effective coating of TAD and polyethyleneimine.
The further proves that the modified plant tannin environment-friendly magnetic flocculant TP @ Fe 3 O 4 The successful preparation.
[ example 9 ] A method for producing a polycarbonate
VSM testing
The VSM test was performed on the sample obtained in example 1, and the result is shown in fig. 6.
As can be seen from the figure, Fe 3 O 4 The saturation magnetization is 84.5emu/g, TP @ Fe 3 O 4 The optimum saturation magnetization of (A) is reduced to 39.1 emu/g. This may be related to the TAD and PEI coverage on the Fe particles. However, 39.1emu/g shows TP @ Fe 3 O 4 The superparamagnetic, magnetic particles of (1) can be separated rapidly.
Step-by-step treatment of algae and algae organic matters in high-algae water body
[ example 10 ]
Environment-friendly magnetic flocculation of modified plant tannin obtained in example 1Initial algal cell density of 1.02X 10 of agent treatment 6 cell/mL of high algae content water.
S1, adding monosulfate into the high algae water body to enable the concentration of the monosulfate to be 100mg/L, and fully mixing to obtain a first water body.
S2, putting the magnetic flocculating agent into the first water body obtained in the step S1 to enable the concentration of the magnetic flocculating agent to be 100mg/L, fully mixing, and then carrying out magnetic separation to separate the cyanobacteria cells in the first water body, so that the algae liquid with the cyanobacteria cells removed, namely the second water body, is obtained.
S3, putting the peroxymonosulfate into the second water body obtained in the step S2 again to enable the concentration of the peroxymonosulfate to be 600mg/L, and performing ultraviolet treatment for 3 hours under the ultraviolet light of 1.15 mW/cm3 to degrade algae organic matters and algae toxins.
After the treatment is finished, the removal efficiency of the algae cells reaches 94%, the DOC removal rate reaches 80%, and the removal rate of the algal toxins reaches 92%.
[ example 11 ]
The initial cell density of the algae treated by the modified plant tannin environment-friendly magnetic flocculant obtained in example 2 is 5.14 multiplied by 10 6 cell/mL of high algae-laden water.
S1, adding monosulfate into the high algae water body to enable the concentration of the monosulfate to be 150mg/L, and fully mixing to obtain a first water body.
S2, putting the magnetic flocculating agent into the first water body obtained in the step S1 to enable the concentration of the magnetic flocculating agent to be 100mg/L, fully mixing, and then carrying out magnetic separation to separate the cyanobacteria cells in the first water body, so that the algae liquid with the cyanobacteria cells removed, namely the second water body, is obtained.
S3, putting the peroxymonosulfate into the second water body obtained in the step S2 again to enable the concentration of the peroxymonosulfate to be 400mg/L, and carrying out ultraviolet irradiation for 4 hours under the ultraviolet light of 1.2 mW/cm3 to degrade organic matters and algal toxins.
After the treatment is finished, the removal efficiency of the algae cells reaches 94%, the DOC removal rate reaches 80%, and the removal rate of the algal toxins reaches 92%.
[ example 12 ]
The initial cell density of the algae treated by the modified plant tannin environment-friendly magnetic flocculant obtained in the example 3 is 1.62 multiplied by 10 7 cell/mL of high algae content water.
S1, adding monosulfate into the high algae water body to enable the concentration of the monosulfate to be 125mg/L, and fully mixing to obtain a first water body.
S2, putting the magnetic flocculating agent into the first water body obtained in the step S1 to enable the concentration of the magnetic flocculating agent to be 150mg/L, fully mixing, and then carrying out magnetic separation to separate the cyanobacteria cells in the first water body, so that the algae liquid with the cyanobacteria cells removed, namely the second water body, is obtained.
S3, putting the peroxymonosulfate into the second water body obtained in the step S2 again to enable the concentration of the peroxymonosulfate to be 100mg/L, and carrying out ultraviolet irradiation for 3.5 hours under the ultraviolet light of 1.2 mW/cm3 to degrade organic matters and algal toxins.
After the treatment is finished, the removal efficiency of the algae cells reaches 98%, the DOC removal rate reaches 70%, and the removal rate of the algal toxins reaches 86%.
[ example 13 ]
The initial cell density of algae treated by the modified plant tannin environment-friendly magnetic flocculant obtained in example 4 is 3.18 multiplied by 10 6 cell/mL of high algae-laden water.
S1, adding monosulfate into the high algae water body to make the concentration of the monosulfate be 150mg/L, and fully mixing to obtain a first water body.
S2, putting the magnetic flocculating agent into the first water body obtained in the step S1 to enable the concentration of the magnetic flocculating agent to be 120mg/L, fully mixing, and then carrying out magnetic separation to separate the cyanobacteria cells in the first water body, so that the algae liquid with the cyanobacteria cells removed, namely the second water body, is obtained.
S3, putting the peroxymonosulfate into the second water body obtained in the step S2 again to enable the concentration of the peroxymonosulfate to be 100mg/L, and carrying out ultraviolet irradiation for 3.5 hours under the ultraviolet light of 1.5 mW/cm3 to degrade organic matters and algal toxins.
After the treatment is finished, the removal efficiency of the algae cells reaches 97%, the DOC removal rate reaches 83%, and the removal rate of the algal toxins reaches 83%.
[ example 14 ]
The initial cell density of the algae treated by the modified plant tannin environment-friendly magnetic flocculant obtained in example 5 is 6.24 multiplied by 10 6 cell/mL of high algae content water.
S1, adding monosulfate into the high algae water body to enable the concentration of the monosulfate to be 130mg/L, and fully mixing to obtain a first water body.
S2, putting the magnetic flocculating agent into the first water body obtained in the step S1 to enable the concentration of the magnetic flocculating agent to be 150mg/L, fully mixing, and then carrying out magnetic separation to separate the cyanobacteria cells in the first water body, so that the algae liquid with the cyanobacteria cells removed, namely the second water body, is obtained.
S3, putting the peroxymonosulfate into the second water body obtained in the step S2 again to enable the concentration of the peroxymonosulfate to be 100mg/L, and carrying out ultraviolet irradiation for 3 hours under the ultraviolet light of 1.3 mW/cm3 to degrade organic matters and algal toxins.
After the treatment is finished, the removal efficiency of the algae cells reaches 90%, the DOC removal rate reaches 83%, and the removal rate of the algal toxins reaches 89%.
In conclusion, the magnetic flocculant can capture algae cells more easily, is small in dosage, is combined with step-by-step treatment of a high algae water body, has the algae cell removal rate of 98 percent, the DOC removal rate of 83 percent and the algal toxin removal rate of 92 percent, can realize high-efficiency removal of the algae cells and rapid and thorough degradation of algae organic matters and algal toxins.
Although the present invention has been described with reference to the preferred embodiments, it is not intended to be limited thereto. Those skilled in the art can make various changes and modifications without departing from the spirit and scope of the invention. Therefore, the protection scope of the present invention should be defined by the appended claims.
Claims (12)
1. The modified plant tannin environment-friendly magnetic flocculant is characterized by comprising ferroferric oxide nanoparticles, wherein the surfaces of the ferroferric oxide nanoparticles are coated with copolymer tannin and polyethyleneimine, and the copolymer tannin is a product of the copolymerization of tannin with acrylamide and methacryloyloxyethyl trimethyl ammonium chloride monomers.
2. The modified plant tannin environment-friendly magnetic flocculant as claimed in claim 1, wherein the particle size of the ferroferric oxide nanoparticles is 50-200 nm.
3. The preparation method of the modified plant tannin environment-friendly magnetic flocculant as claimed in any one of claims 1 to 2, characterized by comprising the following steps:
preparation of copolymerized tannin: dispersing tannin extract in ultrapure water, adding an initiator, and fully activating tannin by the initiator to obtain a first mixed solution;
dropwise adding a mixed aqueous solution of an acrylamide monomer and a methacryloyloxyethyl trimethyl ammonium chloride monomer into the first mixed solution to obtain a second mixed solution, reacting the second mixed solution under the conditions of stirring and water bath, and purifying, cleaning and drying a product obtained after the reaction is finished to obtain a copolymerized tannin TAD;
the preparation method of the modified plant tannin environment-friendly magnetic flocculant comprises the following steps: dissolving TAD and polyethyleneimine in ultrapure water dispersed with ferroferric oxide nanoparticles to obtain a third mixed solution, adding glutaraldehyde into the third mixed solution, carrying out oscillation reaction under the condition of constant-temperature water bath, separating a product obtained after the reaction is finished, washing and drying to obtain the modified plant tannin environment-friendly magnetic flocculant.
4. The method for preparing the modified plant tannin environment-friendly magnetic flocculant as claimed in claim 3, wherein in the first mixed solution, the concentration of the initiator is 0.01-0.02 mol/L, the mass ratio of the initiator to the tannin extract is (1-1.5): 5, and the initiator is Ce (NH) 4 ) 2 (NO 3 ) 6 An aqueous solution.
5. The preparation method of the environment-friendly magnetic flocculant made of modified plant tannin according to claim 3, wherein in the second mixed solution, the mass ratio of acrylamide monomer to tannin extract is (1-3): 1, and the mass ratio of acrylamide monomer to methacryloyloxyethyl trimethyl ammonium chloride monomer is (1-5).
6. The preparation method of the modified plant tannin environment-friendly magnetic flocculant as claimed in claim 3, wherein in the third mixed solution, the mass ratio of ferroferric oxide nanoparticles to TAD is 1 (5-10), and the molar ratio of TAD to polyethyleneimine is (3-5) to 1;
the mass ratio of the volume of the glutaraldehyde to the TAD is (5-10) mL (1.0-2.0) g, and the purity of the glutaraldehyde is 50 wt.%.
7. The use of the modified plant tannin environment-friendly magnetic flocculant as described in any one of claims 1 to 2 in treatment of high algae water.
8. The method for stepwise treating the high algae water body by using the modified plant tannin environment-friendly magnetic flocculant of any one of claims 1 to 2 is characterized by comprising the following steps:
s1, adding monosulfate into the high algae water body, and fully mixing to obtain a first water body;
s2, putting the magnetic flocculating agent into the first water body obtained in the step S1, fully mixing, and then carrying out magnetic separation to separate the cyanobacteria cells in the first water body, so as to obtain a cyanobacteria cell-removed cyanobacteria liquid, namely a second water body;
s3, adding peroxymonosulfate into the second water body obtained in the step S2, reacting under the condition of ultraviolet irradiation, and degrading algae organic matters and algal toxins;
wherein the magnetic flocculant is the modified plant tannin environment-friendly magnetic flocculant in any one of claims 1-2.
9. The method as claimed in claim 8, wherein in step S1, the amount of permonosulfate is determined according to the density of algae in the water body, and the density of algae is 1.11-8.87 x 10 6 The dosage of the peroxymonosulfate is 100-200mg/L at each cell/mL.
10. The method according to claim 8, wherein in step S2, the amount of the magnetic flocculant is determined according to the density of algae in the water body, and the density of algae is 0.11-9.87 x 10 6 When each cell/mL is detected, the dosage of the magnetic flocculant is 10-200 mg/L.
11. The method as claimed in claim 8, wherein in step S3, the adding concentration of peroxymonosulfate is in the range of 400-600 mg/L.
12. The method according to claim 8, wherein in step S3, the ultraviolet irradiation conditions are as follows:
the ultraviolet wavelength range is 200-245nm, and the ultraviolet irradiation intensity>1.15mW/cm 2 The ultraviolet irradiation time range is 3-4 h.
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