CN113321281B - Composite flocculant based on cationic tannin modified clay, preparation method thereof and treatment method of closed water body - Google Patents
Composite flocculant based on cationic tannin modified clay, preparation method thereof and treatment method of closed water body Download PDFInfo
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- CN113321281B CN113321281B CN202110601530.1A CN202110601530A CN113321281B CN 113321281 B CN113321281 B CN 113321281B CN 202110601530 A CN202110601530 A CN 202110601530A CN 113321281 B CN113321281 B CN 113321281B
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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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5263—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using natural chemical compounds
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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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
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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
- C02F7/00—Aeration of stretches of water
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- 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
- Y02W10/10—Biological treatment of water, waste water, or sewage
Abstract
The invention provides a composite flocculant based on cationic tannin modified clay, which has a core-shell structure with cationic tannin as a shell and clay materials as cores; wherein the cationic tannin is prepared by taking vegetable tannin as a base material, ethanolamine or diethanolamine and formaldehyde as raw materials and carrying out Mannich reaction. The invention also provides a preparation method of the composite flocculant based on the cationic tannin modified clay and a treatment method of the closed water body. The composite flocculant has good sedimentation performance, can quickly purify water, is environment-friendly, has less addition amount and low cost, and has good application prospect.
Description
Technical Field
The invention belongs to the technical field of water treatment, and particularly relates to a composite flocculant based on cationic tannin modified clay, a preparation method thereof and a treatment method of closed water.
Background
The closed water body refers to natural or artificially constructed lakes, ponds and the like, has a certain function, and has the characteristics of strong closure, basically no water body flowing and poor self-cleaning function. Because the mobility of water in the closed water body is poor, exogenous pollutants entering the water body and endogenous pollutants generated in the water body can only be degraded by means of self-purification of the water body, and once the total amount of the pollutants exceeds the self-purification capacity of the water body, the water quality can be deteriorated.
The treatment of closed water with deteriorated water quality in the prior art generally comprises the following steps: a source control and sewage interception; removing secondary bottom mud; thirdly, manual repair is performed. Wherein, the common technology of artificial repair comprises the steps of adding biological bacteria, purifying algae, feeding algae, adding aquatic animals, planting aquatic plants, artificially increasing oxygen and the like. Effective water purification techniques often require comprehensive utilization of the above-described techniques. Overall, the treatment difficulty of the water body with deteriorated water quality is high, and the treatment cost is high.
The clay flocculation method is a common natural water quality purification method, which removes water pollutants by adding a large amount of local clay, quickly purifies water, has the advantages of low cost, easy operation and the like, but also has the problems of large adding amount, low efficiency and the like. Various studies have been made by the worldwide scholars regarding the disadvantages of clay flocculation, and it has been found that the flocculation efficiency can be greatly improved by directly or indirectly modifying the clay by combining or applying physical means between the clay and other compounds.
At present, the modification method of clay is mainly divided into two major types of inorganic modification, organic modification and the like, but the modification modes have different advantages and disadvantages. For example, inorganic modification modes such as polyaluminium chloride modified clay flocculant have the characteristics of good flocculation effect, low price and the like, but residual inorganic metal ions can cause environmental risks; the organic modification mode such as the polyacrylamide modified clay flocculant has the advantages of small dosage, strong flocculation capacity and large floc particle size, but the popularization and application of the polyacrylamide modified clay flocculant in water treatment are limited by the difficult degradability and the toxicity of the residual acrylamide monomer.
Vegetable tannins, also known as plant polyphenols, are the secondary generations of complex phenols of plantsA metabolite. The reserves of plant tannins in nature are very abundant, mainly existing in the skin, root, leaf and pulp of plants, and are fourth big forest byproducts next to cellulose, lignin and hemicellulose. The isoelectric point of the natural extracted plant tannin is lower (pH value) pzc =2.0 to 3.0), while natural water colloids and pollutants caused by human activities are usually predominantly electronegative, so cationization modification of vegetable tannins is required. However, the cationic modified tannin still has the problem of poor sedimentation performance, and when the natural water body is treated, the floccule possibly cannot be settled due to the disturbance of stormy waves, so that the flocculation performance of the floccule is affected, and the floccule cannot be recycled.
Therefore, it is necessary to develop a novel flocculant with high efficiency, low cost, environmental protection and strong environmental adaptability.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the composite flocculant based on the cationic tannin modified clay, which has good sedimentation performance, can quickly purify water, is environment-friendly, has less addition amount and low cost, and has good application prospect.
Another object of the present invention is to provide a method for preparing a cationic tannin-modified clay-based composite flocculant.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a composite flocculant based on cationic tannin modified clay has a core-shell structure with cationic tannin as a shell and clay material as a core;
wherein the cationic tannin is prepared by taking vegetable tannin as a base material, ethanolamine or diethanolamine and formaldehyde as raw materials and carrying out Mannich reaction.
Preferably, the clay is kaolin, bentonite, diatomaceous earth or montmorillonite.
A preparation method of a composite flocculant based on cationic tannin modified clay comprises the following steps:
dissolving tannin extract powder in water to prepare tannin solution, heating the tannin solution for the first time, adding a certain volume of ethylenediamine alcohol or ethylenediamine into the tannin solution, stirring and mixing for the first time, and regulating pH to obtain a first mixed solution;
after the first mixed solution is heated for the second time, adding a certain amount of formaldehyde into the first mixed solution to obtain a second mixed solution, heating the second mixed solution for the third time, and continuously stirring for the second time to react; after the second stirring is finished, adding pure water into the second mixed solution to obtain cationic tannin;
weighing a certain amount of cationic tannin and clay, adding pure water, and stirring until the cationic tannin and the clay are fully dissolved and dispersed to obtain a third mixed solution; slowly dripping a cross-linking agent into the third mixed solution to fully react; and after the reaction is finished, adding ethanol into the reaction product to carry out dehydration embrittlement, and then carrying out vacuum drying, crushing and grinding to obtain the composite flocculant of the cationic tannin modified clay.
Preferably, the tannin extract has a tannin content of 40-70%.
Preferably, the mass ratio of the addition volume of the diethanolamine to the addition of the tannin extract is (19.4-23.4): 5.
Preferably, the mass ratio of the addition volume of the ethanolamine to the addition of the tannin extract is (7.8-11.8): 5.
Preferably, the mass ratio of the formaldehyde to the tannin extract is (3.8-23.8): 25.
Preferably, the mass ratio of the cationic vegetable tannin to the clay is 1:1-10:1.
Preferably, the cross-linking agent is epichlorohydrin and the amount is 0.05 to 5wt.% of the cationic tannin.
Preferably, the first temperature is raised to 65-75 ℃, the second temperature is raised to 75-85 ℃, and the third temperature is raised to 85-90 ℃;
after the first stirring and mixing, regulating the pH to 6-7 to obtain a first mixed solution; the time of the first stirring and the second stirring is more than or equal to 3 hours; slowly dripping a cross-linking agent into the third mixed solution, wherein the time of full reaction is more than or equal to 12 hours.
The third aspect of the invention aims to provide a method for treating a closed black and odorous water body, which comprises the following steps: arranging a plurality of rows of micro-nano aeration devices at the water bottom of the water body to be treated along the water flow vertical direction, and preparing a treating agent into a treating agent stock solution; then aeration is carried out to ensure the dissolved oxygen in the water body, and then the treating agent stock solution is uniformly added into the water body to be treated, wherein the adding speed is higher than the water flow speed; wherein the treating agent is the composite flocculant based on the cationic tannin modified clay.
Preferably, after the treatment agent is added, the concentration of the treatment agent in the water body meets the following conditions: the amount of the treating agent in each milliliter of water body is 50-100 mg.
Preferably, each row of micro-nano aeration devices is provided with one micro-nano aeration head every 20m, each micro-nano aeration device is provided with three micro-nano aeration heads, each aeration is performed for 12 hours in an interval aeration mode, and the interval is 2 hours after each two times of aeration, so that the dissolved oxygen of the water body is ensured to be more than 5 mg/L.
The invention has the beneficial effects that:
1. the composite flocculant has a core-shell structure with cationic tannin as a shell and clay material as a core, can remove a large amount of pollutants such as suspended matters, algae and the like, quickly purifies water, and remarkably improves water quality; in addition, the flocs can be rapidly separated after the treatment is finished, and can be recycled, so that the solid-liquid separation capacity is improved, and meanwhile, the cost is effectively reduced. Meanwhile, the composite flocculant has small dosage, thereby reducing the sludge yield and the subsequent treatment cost.
2. The tannin used in the composite flocculant is a biodegradable material, the clay is an inorganic mineral material, and the composite flocculant has the advantages of no harm, no secondary pollution and the like, so that the composite flocculant is environment-friendly in use, and has good application prospects in the fields of treatment of natural water bodies such as micro-polluted landscape water bodies, black and odorous water bodies, high-algae water bodies and the like and sewage and wastewater treatment.
3. The preparation method of the composite flocculant has the advantages of simple process, easy operation and low cost, and is suitable for further industrial production and application.
Drawings
FIG. 1 is a ZETA potential diagram of the tannin, cationic tannin and cationic tannin modified clay composite flocculant of example 1.
FIG. 2 is a graph showing the effect of the cationic tannin modified clay composite flocculant in example 1 on treating a kaolin suspension.
FIG. 3 is a graph showing the effect of the cationic tannin modified clay composite flocculant in example 2 on treating a kaolin suspension.
Detailed Description
For a better understanding of the technical content of the present invention, specific examples are set forth below, along with the accompanying drawings.
Aspects of the invention are described in this disclosure with reference to the drawings, in which are shown a number of illustrative embodiments. The 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 more detail below, may be implemented in any of a wide variety of ways.
According to the composite flocculant based on the cationic tannin modified clay, provided by the exemplary embodiment of the invention, the composite flocculant is used for removing suspended matters, algae and other pollutants in water, the sedimentation performance of the flocs is improved through the composite material formed by the clay and the cationic tannin, the water is rapidly purified, the composite flocculant can be recycled, secondary pollution is avoided, and the composite flocculant is environment-friendly and has good application prospects in the fields of treatment of natural water bodies such as micro-polluted landscape water bodies, black and odorous water bodies, high algae water bodies and sewage and wastewater treatment.
The composite flocculant based on the cationic tannin modified clay according to the exemplary embodiment of the present invention has a core-shell structure with cationic tannin as a shell and clay material as a core; wherein the cationic tannin is prepared by taking vegetable tannin as a base material, ethanolamine or diethanolamine and formaldehyde as raw materials and carrying out Mannich reaction.
In a preferred embodiment, the clay is kaolin, bentonite, diatomaceous earth or montmorillonite.
According to the disclosed examples, the invention provides a preparation method of a composite flocculant based on cationic tannin modified clay, which comprises the following steps:
dissolving tannin extract powder in 5-10 mL of pure water, slowly adding tannin extract in batches, fully stirring to avoid tannin aggregation and ensure complete dissolution, preparing tannin solution, heating the tannin solution for the first time, adding a certain volume of ethylenediamine alcohol or ethylenediamine into the tannin solution, stirring and mixing for the first time, and regulating pH to obtain a first mixed solution;
after the first mixed solution is heated for the second time, adding a certain amount of formaldehyde into the first mixed solution to obtain a second mixed solution, heating the second mixed solution for the third time, and continuously stirring for the second time to react; after the second stirring is finished, adding 5-10 mL of pure water into the second mixed solution to obtain cationic tannin;
weighing a certain amount of cationic tannin and clay, adding 30-70 mL of pure water, and stirring until the cationic tannin and the clay are fully dissolved and dispersed to obtain a third mixed solution; slowly dripping a cross-linking agent into the third mixed solution to fully react; and after the reaction is finished, adding ethanol into the reaction product to carry out dehydration embrittlement, and then carrying out vacuum drying, crushing and grinding to obtain the composite flocculant of the cationic tannin modified clay.
Preferably, the tannin extract has a tannin content of 40-70%.
Preferably, the mass ratio of the addition volume of the diethanolamine to the addition of the tannin extract is (19.4-23.4): 5.
Preferably, the mass ratio of the addition volume of the ethanolamine to the addition of the tannin extract is (7.8-11.8): 5.
Preferably, the mass ratio of the formaldehyde to the tannin extract is (3.8-23.8): 25.
Preferably, the mass ratio of the cationic vegetable tannin to the clay is 1:1-10:1.
Preferably, the cross-linking agent is epichlorohydrin and the amount is 0.05 to 5wt.% of the cationic tannin.
Preferably, the first temperature is raised to 65-75 ℃, the second temperature is raised to 75-85 ℃, and the third temperature is raised to 85-90 ℃.
Preferably, after the first stirring and mixing, regulating the pH to 6-7 to obtain a first mixed solution; the time of the first stirring and the second stirring is more than or equal to 3 hours; slowly dripping a cross-linking agent into the third mixed solution, wherein the time of full reaction is more than or equal to 12 hours.
The invention also provides an in-situ treatment method of black and odorous water bodies of town river channels, which comprises the following steps: arranging a plurality of rows of micro-nano aeration devices at the water bottom of the water body to be treated along the water flow vertical direction, and preparing a treating agent into a treating agent stock solution; then aeration is carried out to ensure the dissolved oxygen in the water body, and then the treating agent stock solution is uniformly added into the water body to be treated, wherein the adding speed is higher than the water flow speed; wherein the treating agent is the composite flocculant based on the cationic tannin modified clay.
In a preferred embodiment, after the treatment agent is added, the conditions for the concentration of the treatment agent in the water body are as follows: the amount of the treating agent in each milliliter of water body is 50-100 mg.
In another preferred embodiment, each row of micro-nano aeration devices is arranged every 20m, each micro-nano aeration device is provided with three micro-nano aeration heads, and the aeration is performed for 12h each time in an interval aeration mode, and the interval is 2h after each two times of aeration, so that the dissolved oxygen of the water body is ensured to be more than 5 mg/L.
It should be understood that the composite flocculant of the present invention includes, but is not limited to, enclosed water bodies that meet the treatment of various desirable water bodies, such as micro-polluted landscape water bodies, high algae water bodies, and the like.
For a better understanding, the present invention will be further described with reference to several specific examples, but the preparation process is not limited thereto, and the present invention is not limited thereto.
[ example 1 ]
2.5g tannin extract powder was dissolved in 5mL of pure water. The tannin extract is slowly added in batches and fully stirred to avoid tannin aggregation and ensure complete dissolution; heating the tannin solution to 70 ℃, adding 10.7mL of diethanolamine, magnetically stirring for 3 hours to fully mix the tannin solution, and adjusting the pH of the solution to 6.5 by using concentrated hydrochloric acid with the mass concentration of 37%; heating the tannin mixed solution to 80 ℃, slowly adding 1.38mL of formaldehyde by a peristaltic pump, then raising the temperature of the solution to 85 ℃ again, and continuously stirring for 3 hours; after stirring, adding 5mL of pure water to stop the reaction to obtain the cationic vegetable tannin; weighing 2g of cationic vegetable tannin and 20g of clay, putting into a 100mL three-necked flask filled with 50mL of pure water, and stirring for 1h to fully dissolve and disperse; slowly dropwise adding 0.1g of epichlorohydrin into the obtained solution, and fully reacting for 12 hours; and after the reaction is finished, adding ethanol into the product to dehydrate and embrittle, and then carrying out vacuum drying, crushing and grinding to obtain the cationic tannin modified clay composite flocculant.
The ZETA potential diagram of the black Jing Shushan Nile and the resulting cationic black Jing Shushan Nile flocculant is shown in FIG. 1, and it can be seen that the isoelectric point of the cationic black Jing Shushan Nile flocculant is significantly higher than that of black Jing Shushan Nile, the flocculant is positively charged over a wider pH range, and the pH range for removal of negatively charged contaminants is wider.
The composite flocculant is tested for kaolin removal performance, and as shown in fig. 2, the flocculant reduces the turbidity of a kaolin suspension with an initial turbidity of 25.2NTU to 2.5NTU at an addition amount of 50mg/L, and the sedimentation time is less than 5min, which indicates that the composite flocculant has better pollutant removal capability and good sedimentation property.
[ example 2 ]
2.5g tannin extract powder was dissolved in 5mL of pure water. The tannin extract is slowly added in batches and fully stirred to avoid tannin aggregation and ensure complete dissolution; heating the tannin solution to 70 ℃, adding 4.9mL of ethanolamine, magnetically stirring for 3h to fully mix the tannin solution, and adjusting the pH of the solution to 6.5 by using concentrated hydrochloric acid with the mass concentration of 37%; heating the tannin mixed solution to 80 ℃, slowly adding 1.38mL of formaldehyde by a peristaltic pump, then raising the temperature of the solution to 90 ℃ again, and continuously stirring for 3 hours; after stirring, adding 5mL of pure water to stop the reaction to obtain the cationic vegetable tannin; weighing 2g of cationic vegetable tannin and 2g of clay, putting into a 100mL three-necked flask filled with 50mL of pure water, and stirring for 1h to fully dissolve and disperse; slowly dripping 0.5g of epichlorohydrin into the obtained solution, and fully reacting for 12 hours; and after the reaction is finished, adding ethanol into the product to dehydrate and embrittle, and then carrying out vacuum drying, crushing and grinding to obtain the cationic tannin modified clay composite flocculant.
The performance of the flocculant to remove kaolin was tested and the flocculant was used to reduce the turbidity of a kaolin suspension having an initial turbidity of 25NTU to 2.6NTU for less than 5 minutes at 25mg/L dosage as shown in figure 3. The composite flocculant has better pollutant removal capability and good sedimentation property.
[ example 3 ]
2.5g tannin extract powder was dissolved in 5mL of pure water. The tannin extract is slowly added in batches and fully stirred to avoid tannin aggregation and ensure complete dissolution; heating the tannin solution to 75 ℃, adding 9.7mL of diethanolamine, magnetically stirring for 3 hours to fully mix the tannin solution, and adjusting the pH of the solution to 6.5 by using concentrated hydrochloric acid with the mass concentration of 37%; heating the tannin mixed solution to 85 ℃, slowly adding 2.38mL of formaldehyde by a peristaltic pump, then raising the temperature of the solution to 90 ℃ again, and continuously stirring for 3 hours; after stirring, adding 5mL of pure water to stop the reaction to obtain the cationic vegetable tannin; weighing 2g of cationic vegetable tannin and 20g of clay, putting into a 100mL three-necked flask filled with 50mL of pure water, and stirring for 1h to fully dissolve and disperse; slowly dripping 0.125g of epichlorohydrin into the obtained solution, and fully reacting for 12 hours; and after the reaction is finished, adding ethanol into the product to dehydrate and embrittle, and then carrying out vacuum drying, crushing and grinding to obtain the cationic tannin modified clay composite flocculant.
The performance of the flocculant for removing kaolin is tested, and the flocculant reduces the turbidity of the kaolin suspension with initial turbidity of 50NTU to 4NTU at the dosage of 20mg/L, and the sedimentation time is less than 5min. The composite flocculant has better pollutant removal capability and good sedimentation property.
[ example 4 ]
2.5g tannin extract powder was dissolved in 5mL of pure water. The tannin extract is slowly added in batches and fully stirred to avoid tannin aggregation and ensure complete dissolution; heating the tannin solution to 65 ℃, adding 3.9mL of ethanolamine, magnetically stirring for 3 hours to fully mix the tannin solution, and adjusting the pH of the solution to 6.5 by using concentrated hydrochloric acid with the mass concentration of 37%; heating the tannin mixed solution to 75 ℃, slowly adding 0.38mL of formaldehyde by a peristaltic pump, then raising the temperature of the solution to 85 ℃ again, and continuously stirring for 3 hours; after stirring, adding 5mL of pure water to stop the reaction to obtain the cationic vegetable tannin; weighing 2g of cationic vegetable tannin and 2g of clay, putting into a 100mL three-necked flask filled with 50mL of pure water, and stirring for 1h to fully dissolve and disperse; slowly dripping 0.0125g of epichlorohydrin into the obtained solution, and fully reacting for 12 hours; and after the reaction is finished, adding ethanol into the product to dehydrate and embrittle, and then carrying out vacuum drying, crushing and grinding to obtain the cationic tannin modified clay composite flocculant.
The performance of the flocculant in removing kaolin was tested, and the flocculant was added at 30mg/L to reduce the turbidity of a kaolin suspension having an initial turbidity of 50NTU to 2.3NTU for a settling time of less than 4 minutes. The composite flocculant has better pollutant removal capability and good sedimentation property.
While the invention has been described with reference to preferred embodiments, it is not intended to be limiting. Those skilled in the art will appreciate that various modifications and adaptations can be made without departing from the spirit and scope of the present invention. Accordingly, the scope of the invention is defined by the appended claims.
Claims (11)
1. The composite flocculant based on the cationic tannin modified clay is characterized by having a core-shell structure with cationic tannin as a shell and clay materials as cores;
wherein the cationic tannin is prepared by taking vegetable tannin as a base material, ethanolamine or diethanolamine and formaldehyde as raw materials and carrying out Mannich reaction;
the clay is kaolin, bentonite, diatomite or montmorillonite;
the composite flocculant comprises the following preparation steps:
dissolving tannin extract powder in water to prepare tannin solution, heating the tannin solution for the first time, adding a certain volume of ethanolamine or diethanolamine into the tannin solution, stirring and mixing for the first time, and regulating pH to obtain a first mixed solution;
after the first mixed solution is heated for the second time, adding a certain amount of formaldehyde into the first mixed solution to obtain a second mixed solution, heating the second mixed solution for the third time, and continuously stirring for the second time to react; after the second stirring is finished, adding pure water into the second mixed solution to obtain cationic tannin;
weighing a certain amount of cationic tannin and clay, adding pure water, stirring until the cationic tannin and the clay are fully dissolved and dispersed to obtain a third mixed solution, slowly dripping a cross-linking agent into the third mixed solution, and fully reacting; and after the reaction is finished, adding ethanol into the reaction product to carry out dehydration embrittlement, and then carrying out vacuum drying, crushing and grinding to obtain the composite flocculant of the cationic tannin modified clay.
2. The cationic tannin modified clay-based composite flocculant according to claim 1, wherein the tannin extract has a tannin content of 40 to 70%.
3. The cationic tannin modified clay-based composite flocculant according to claim 1, wherein the addition volume of diethanolamine to the addition mass ratio of tannin extract is (19.4-23.4) mL/5 g.
4. The cationic tannin modified clay-based composite flocculant according to claim 1, wherein the addition volume of ethanolamine and the addition mass ratio of tannin extract are (7.8-11.8) mL/5 g.
5. The cationic tannin modified clay-based composite flocculant according to claim 1, wherein the addition volume of formaldehyde and the addition mass ratio of tannin extract is (3.8-23.8) mL/25 g.
6. The cationic tannin modified clay-based composite flocculant of claim 1, wherein a mass ratio of the cationic tannin to the clay is 1:1 to 10:1.
7. The cationic tannin modified clay-based composite flocculant according to claim 1, wherein the crosslinking agent is epichlorohydrin in an amount of 0.05 to 5wt.% of the cationic tannin.
8. The cationic tannin modified clay-based composite flocculant according to claim 1, wherein the first temperature is raised to 65-75 ℃, the second temperature is raised to 75-85 ℃, and the third temperature is raised to 85-90 ℃;
after the first stirring and mixing, regulating the pH to 6-7 to obtain a first mixed solution; the time of the first stirring and the second stirring is more than or equal to 3 hours; slowly dripping a cross-linking agent into the third mixed solution, wherein the time of full reaction is more than or equal to 12 hours.
9. The method for treating the closed black and odorous water body is characterized by comprising the following steps of: arranging a plurality of rows of micro-nano aeration devices at the water bottom of the water body to be treated along the water flow vertical direction, and preparing a treating agent into a treating agent stock solution; then aeration is carried out to ensure the dissolved oxygen in the water body, and then the treating agent stock solution is uniformly added into the water body to be treated, wherein the adding speed is higher than the water flow speed; wherein the treating agent is the cationic tannin modified clay-based composite flocculant as defined in any one of claims 1 to 8.
10. The method for treating a closed black and odorous water body according to claim 9, wherein after the treating agent is added, the condition of the concentration of the treating agent in the water body is: the amount of the treating agent in each milliliter of water body is 50-100 mg.
11. The method for treating the closed black and odorous water body according to claim 9, wherein each row of micro-nano aeration devices is provided with three micro-nano aeration heads at intervals of 20m, each micro-nano aeration device is aerated for 12h at intervals, and the interval between each two times of aeration is 2h, so that the dissolved oxygen of the water body is ensured to be more than 5 mg/L.
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| CN114956278B (en) * | 2022-06-09 | 2023-06-02 | 河海大学 | Modified plant tannin environment-friendly magnetic flocculant and method for treating high algae water in steps |
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| GB1214532A (en) * | 1967-02-16 | 1970-12-02 | Simonacco Ltd | Improvements in or relating to the treatment of aqueous materials |
| US5846436A (en) * | 1993-06-22 | 1998-12-08 | Betzdearborn Inc. | Composition and method for water clarification |
| US20050061750A1 (en) * | 2003-09-23 | 2005-03-24 | Polymer Ventures, Inc. | Methods for the purification of contaminated waters |
| CN106219696B (en) * | 2016-08-12 | 2018-07-13 | 伍德广聚（北京）环境科技有限公司 | A kind of composite flocculation agent |
| CN107986412B (en) * | 2017-12-28 | 2020-11-03 | 中国科学院海洋研究所 | Modified clay system for controlling harmful algal blooms in aquaculture water |
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| CN112441655A (en) * | 2020-11-06 | 2021-03-05 | 河海大学 | Cationic tannin flocculant for black wattle and preparation method thereof |
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